Agent for altering the color of keratin fibers containing a fatty substance, a rheology modifying polymer, and direct dyes in a cream emulsion system

ABSTRACT

The present invention is drawn to an agent and process for altering the color of keratin fibers wherein the agent comprises: (A) a color base composition, containing from about 50% to about 80% by weight of a fatty substance comprising a fatty substance having a viscosity greater than about 50 mm 2 /s at 40° C.; and optionally, an additional fatty substance; a rheology modifying polymer; and an alkalizing agent; a short alkyl chain hydroxy compound chosen from monoalcohols and polyols; a direct dye; optionally an oxidative dye precursor; and (B) optionally, an oxidizing composition comprising an oxidizing agent.

FIELD OF THE INVENTION

The present invention relates to an agent for altering the color ofkeratinous substrates, including human keratin fibers such as the hair.The agent for altering the color of keratin fibers comprises a fattysubstance, a rheology modifying polymer, direct dyes, optionally,oxidative dyes and optionally, an oxidizing agent.

BACKGROUND OF THE INVENTION

It is known that consumers desire to use cosmetic and personal carecompositions that enhance the appearance of keratin fibers such as hairby changing the color of the hair and/or by imparting various propertiesto hair such as shine and conditioning. The process of changing thecolor of hair can involve either depositing an artificial color onto thehair which provides a different shade or color to the hair or liftingthe color of the hair, such as for example, from a dark brown shade to amedium brown or a light brown shade.

Conventional hair coloring products include permanent hair dyeingproducts, also known as oxidation dyeing, which use the combination ofcompositions containing oxidative dye precursors, also known as primaryintermediates or oxidation bases, and oxidizing products containingoxidizing agents such as peroxide and persulfate compounds, underalkaline pH conditions in the vast majority of cases. In general, theoxidation dye precursors comprise oxidation bases chosen from ortho- orpara-phenylenediamines, ortho- or para-aminophenols, and heterocycliccompounds. These oxidation bases are colorless or weakly coloredcompounds, which, when combined with oxidizing products, can give accessto colored species via a process of oxidative condensation. The shadesobtained with these oxidation bases may often be varied by combiningthem with at least one coupler chosen, for example, from aromaticmeta-diamines, meta-aminophenols, meta-diphenols, and certainheterocyclic compounds, such as indole compounds. The variety ofmolecules used as oxidation bases and couplers can allow a wide range ofcolors to be obtained.

Oxidative coloring compositions typically contain aqueous ammonia as analkalizing agent and for activating the oxidizing agent. Thesealkalizing agents also cause the hair shaft to swell, thus allowing thesmall oxidative dye molecules to penetrate the cuticle and cortex beforethe oxidation condensation process is completed. The resultinglarger-sized colored complexes from the oxidative reaction are thentrapped inside the hair fiber, thereby permanently altering the color ofthe hair. However, the use of ammonia may affect the user, not onlybecause of the undesirable odor of ammonia, but because it may also posegreater risks of intolerance, for instance, irritation of the scalp andstinging.

The option of replacing all or at least some of the aqueous ammonia withat least one other standard alkalizing agent frequently does not lead tocompositions that are as efficient as those based on aqueous ammonia,for example since these alkalizing agents may not afford sufficientlightening of pigmented fibers in the presence of an oxidizing agent.

It is also known practice to dye keratin fibers by direct dyeing. Theprocess conventionally used in direct dyeing comprises applying to thekeratin fibers direct dyes, which are colored and coloring moleculesthat have affinity for the fibers, leaving the dyes to act in order toallow the colored molecules to penetrate, by diffusion, into the hair,and then rinsing the fibers.

In contrast with oxidation dye compositions, direct dye compositions maybe used without the obligatory presence of an oxidizing agent. Inaddition, these direct dyeing operations may be performed repeatedlywithout degrading the keratin fiber.

It is known practice, for example, to use direct dyes of thenitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine,azine, and triarylmethane dyes. Oxidative dye compounds and oxidizingagents as described above may optionally be used in direct dyeingcompositions.

The leave-on time of a direct dye composition conventionally ranges from15 to 45 minutes, depending on the nature of the fiber (sensitized ornon-sensitized) and the nature of the dye used. A great deal of researchhas been conducted on reducing the leave-on time of dye compositionswithout, however, increasing the concentration of the constituents,while at the same time maintaining a good level of dyeing, i.e., gooddyeing power and good fastness of the color with respect to externalagents and over time.

Thus, it would be useful to provide direct dye compositions that areimproved in terms of efficacy and speed of reaction and/or ofpenetration of the dye into the fiber, while at the same timemaintaining good harmlessness, good resistance, and good selectivity,the latter resulting from the difference in color uptake betweendifferent parts of a hair or of a head of hair.

In order to improve the performance of such hair coloring compositions,the use of new and additional ingredients and novel combinations ofingredients are continuously sought; however, the choice of ingredientscould pose difficulties insofar as they must improve the dyeing/liftingcapability of the composition without being detrimental to otherproperties of the composition such as its application, rheology orviscosity properties, stability and/or resulting into more disadvantagessuch as increased damage or a less healthy look to the hair.

It is also important to provide hair coloring compositions with varioustypes of consistency, such that the compositions can be provided in theform of a liquid emulsion, such as a liquid-lotion, liquid-gel,liquid-cream, or a cream emulsion, such as a thick cream or gel-cream,or a foam or mousse wherein the liquid emulsion form has a thinnerconsistency than the cream emulsion form and is typically packaged in abottle. The liquid emulsion form is generally employed when the entirehead of hair is to be colored or when only one color is desired sincethe dye composition spreads easily, allowing for greater coverage whilethe cream emulsion form can be employed for dyeing the entire head ofhair and for highlighting or lightening only certain sections of thehair.

Thus, the objective of the present invention is to obtain novelcompositions for oxidatively dyeing the hair. Another objective of theinvention is to obtain hair coloring compositions that have a unique,non-drip consistency or rheology and yet spreads easily on the hairwhile imparting other advantages to the hair such as conditioning, ahealthy appearance, shine and less damage to the hair.

BRIEF SUMMARY OF THE INVENTION

In order to achieve these and other advantages, the present invention isdrawn to an agent for altering the color of keratin fibers comprising:

(A) a color base composition, containing, in a cosmetically acceptablemedium:

-   -   (a) from about 50% to about 80% by weight of a fatty substance        or a mixture of fatty substances comprising:        -   (i) at least 5% by weight of at least one fatty substance            having a viscosity greater than about 50 mm²/s at 40° C.;            and        -   (ii) from 0% to about 75% by weight of at least one            additional fatty substance other than (A)(a); all weights            being based on the total weight of (A);    -   (b) at least one rheology modifying polymer chosen from:        -   (i) a slightly alkali-swellable cross-linked acrylate            polymer contained in an aqueous dispersion comprising about            30% by weight of total solids; and        -   (ii) a cross-linked anionic acrylate polymer contained in an            aqueous dispersion comprising about 32% by weight of total            solids; and    -   (c) at least one alkalizing agent;    -   (d) at least one short alkyl chain hydroxy compound chosen from        monoalcohols and polyols;    -   (e) at least one direct dye;    -   (f) optionally, at least one oxidative dye precursor; and

(B) optionally, an oxidizing composition comprising, in a cosmeticallyacceptable medium, at least one oxidizing agent.

The present invention is also drawn to a process of coloring keratinousfibers, comprising applying onto the keratin fibers the above-disclosedagent for altering the color of keratin fibers, such as hair, comprisingapplying said agent onto the fibers; and leaving said agent on thekeratin fibers for a period of time sufficient to color the fibers.

DETAILED DESCRIPTION OF THE INVENTION

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients and/or reaction conditionsare to be understood as being modified in all instances by the term“about” which encompasses ±10%.

“At least one” as used herein means one or more and thus includesindividual components as well as mixtures/combinations.

“Keratinous fiber” may be chosen from, for example, human hair.

“Formed from,” as used herein, means obtained from chemical reaction of,wherein “chemical reaction,” includes spontaneous chemical reactions andinduced chemical reactions. As used herein, the phrase “formed from”, isopen ended and does not limit the components of the composition to thoselisted, e.g., as component (i) and component (ii). Furthermore, thephrase “formed from” does not limit the order of adding components tothe composition or require that the listed components (e.g., components(i) and (ii)) be added to the composition before any other components.

“Hydrocarbons,” as used herein, include alkanes, alkenes, and alkynes,wherein the alkanes comprise at least one carbon, and the alkenes andalkynes each comprise at least two carbons; further wherein thehydrocarbons may be chosen from linear hydrocarbons, branchedhydrocarbons, and cyclic hydrocarbons; further wherein the hydrocarbonsmay optionally be substituted; and further wherein the hydrocarbons mayoptionally further comprise at least one heteroatom intercalated in thehydrocarbon chain.

“Silicone compound,” as used herein, includes, for example, silica,silanes, silazanes, siloxanes, and organosiloxanes; and refers to acompound comprising at least one silicon; wherein the silicone compoundmay be chosen from linear silicone compounds, branched siliconecompounds, and cyclic silicone compounds; further wherein the siliconecompound may optionally be substituted; and further wherein the siliconecompound may optionally further comprise at least one heteroatomintercalated in the silicone chain, wherein the at least one heteroatomis different from the at least one silicon.

“Substituted,” as used herein, means comprising at least onesubstituent. Non-limiting examples of substituents include atoms, suchas oxygen atoms and nitrogen atoms, as well as functional groups, suchas hydroxyl groups, ether groups, alkoxy groups, acyloxyalkyl groups,oxyalkylene groups, polyoxyalkylene groups, carboxylic acid groups,amine groups, acylamino groups, amide groups, halogen containing groups,ester groups, thiol groups, sulphonate groups, thiosulphate groups,siloxane groups, and polysiloxane groups. The substituent(s) may befurther substituted.

“Polymers,” as defined herein, include homopolymers and copolymersformed from at least two different types of monomers.

The term “substantially free of ammonia” as defined herein means thatthe compositions or agent for altering the color of keratin fibers ofthe present invention is either completely free of ammonia (includingammonium ions) or contains no appreciable amount of ammonia (includingammonium ions), for example, no more than 1% by weight, or no more than0.5% by weight, or no more than 0.3% by weight, or no more than 0.1% byweight, based on the weight of the compositions or agent for alteringthe color of keratinous substrates.

It has been surprisingly and unexpectedly discovered that when the colorbase and oxidizing compositions were mixed, the resulting agent foraltering the color of keratin fibers (also called ready-to-usecomposition) had improved dyeing properties. For example, the agent foraltering the color of keratin fibers provided coloring with goodstrength and/or intensity and/or good uniformity of the color along thefiber between the tip and the root of the hair (also called theselectivity of coloring) and/or good chromaticity. In addition, theagent for altering the color of keratin fibers can be applied withoutdifficulty onto keratin fibers without running or dripping.

It has also been surprisingly and unexpectedly found that the color ofhair can be effectively altered according to the present disclosure at alowered cost and less time of production because lower amounts of dyecompounds can be employed and the color base composition of the presentinvention can be prepared without the use of heat or using a coldprocess method.

Fatty Substances

The color base composition or the color base composition of the presentinvention comprises at least one fatty substance having a viscosity ofgreater than about 50 mm²/s at 40° C.

The viscosity of the at least one fatty substance having a viscosity ofgreater than about 50 mm²/s at 40° C. of the present invention ismeasured as kinematic viscosity according to the ASTM D 445 method andmay range from between greater than about 50 to about 100 mm²/s at 40°C., preferably from about 50 to about 100 mm²/s at 40° C.

The at least one fatty substance having a viscosity of greater thanabout 50 mm²/s at 40° C. may be chosen from oils such as mineral oil(kinematic viscosity as measured by the ASTM D 445 method in units ofmm²/s at 40° C.).

A preferred fatty substance having a viscosity of greater than 50 mm²/sat 40° C. is a mineral oil having a viscosity ranging from between about63 to about 70 mm²/s at 40° C., commercially available from the supplierSonneborn under the tradename Kaydol® Heavy White Mineral Oil or fromthe supplier Exxonmobil Chemical under the tradename Primol™ 352.

The at least one fatty substance having a viscosity of greater thanabout 50 mm²/s at 40° C. may also be referred to hereinafter as “highviscosity mineral oil.”

The color base composition of the present invention may further comprisean additional fatty substance other than the fatty substance having aviscosity of greater than about 50 mm²/s/at 40° C.

“Fatty substance” means an organic compound insoluble in water at normaltemperature (25° C.) and at atmospheric pressure (750 mmHg) (solubilitybelow 5% and such as below 1% and further such as below 0.1%). Fattysubstances have in their structure a chain of at least two siloxanegroups or at least one hydrocarbon chain having at least 6 carbon atoms.Moreover, fatty substances are generally soluble in organic solvents inthe same conditions of temperature and pressure, for example inchloroform, ethanol, benzene or decamethylcyclopentasiloxane.

Fatty substances are, for example, chosen from lower alkanes, fattyalcohols, esters of fatty acid, esters of fatty alcohol, oils such asmineral, vegetable, animal and synthetic non-silicone oils, non-siliconewaxes and silicones.

In some embodiments, the alcohols and esters have at least one linear orbranched, saturated or unsaturated hydrocarbon group, comprising 6 to 30carbon atoms, optionally substituted, for example, with at least onehydroxyl group (for example 1 to 4). If they are unsaturated, thesecompounds can have one to three, conjugated or unconjugated,carbon-carbon double bonds.

With regard to the lower alkanes, in some embodiments, these have from 6to 16 carbon atoms and are linear or branched, optionally cyclic. Asexamples, alkanes can be chosen from hexane and dodecane, isoparaffinssuch as isohexadecane and isodecane.

Non-limiting examples of non-silicone oils usable in the composition ofthe disclosure, include: hydrocarbon oils of animal origin, such asperhydrosqualene; hydrocarbon oils of vegetable origin, such as liquidtriglycerides of fatty acids having from 6 to 30 carbon atoms such astriglycerides of heptanoic or octanoic acids, or for example sunfloweroil, maize oil, soya oil, cucurbit oil, grapeseed oil, sesame oil,hazelnut oil, apricot oil, macadamia oil, arara oil, sunflower oil,castor oil, avocado oil, triglycerides of caprylic/capric acids such asthose sold by the company Stearineries Dubois or those sold under thenames MIGLYOL® 810, 812 and 818 by the company Dynamit Nobel, jojobaoil, shea butter oil; hydrocarbons with more than 16 carbon atoms,linear or branched, of mineral or synthetic origin, such as paraffinoils, petroleum jelly, liquid paraffin, polydecenes, hydrogenatedpolyisobutene such as Parleam®. fluorinated, partially hydrocarbon oils;as fluorinated oils, non-limiting examples includeperfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, soldunder the names “FLUTEC® PC1” and “FLUTEC® PC3” by the company BNFLFluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanessuch as dodecafluoropentane and tetradecafluorohexane, sold under thenames “PF 5050®” and “PF 5060®” by the 3M Company, orbromoperfluorooctyl sold under the name “FORALKYL®” by the companyAtochem; nonafluoro-methoxybutane and nonafluoroethoxyisobutane;derivatives of perfluoromorpholine, such as 4-trifluoromethylperfluoromorpholine sold under the name “PF 5052®” by the 3M Company.

The fatty alcohols usable as fatty substances in the composition of thedisclosure include, but are not limited to, non-alkoxylated, saturatedor unsaturated, linear or branched, and have from 6 to 30 carbon atomsand more particularly from 8 to 30 carbon atoms; For example, cetylalcohol, stearyl alcohol and their mixture (cetylstearyl alcohol),octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol,oleic alcohol or linoleic alcohol.

The exemplary non-silicone wax or waxes that can be used in thecomposition of the disclosure are chosen from carnauba wax, candelillawax, and Alfa wax, paraffin wax, ozokerite, vegetable waxes such asolive wax, rice wax, hydrogenated jojoba wax or absolute waxes offlowers such as the essential wax of blackcurrant flower sold by thecompany BERTIN (France), animal waxes such as beeswaxes, or modifiedbeeswaxes (cerabellina); other waxes or waxy raw materials usableaccording to the disclosure are, for example, marine waxes such as thatsold by the company SOPHIM under reference M82, waxes of polyethylene orof polyolefins in general.

The exemplary fatty acid esters are the esters of saturated orunsaturated, linear or branched C₁-C₂₆ aliphatic mono- or polyacids andof saturated or unsaturated, linear or branched C₁-C₂₆ aliphatic mono-or polyalcohols, the total number of carbons of the esters being, forexample, greater than or equal to 10.

Among the monoesters, non-limiting mentions can be made ofdihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyllactate; C₁₂-C₁₅ alkyl lactate; isostearyl lactate; lauryl lactate;linoleyl lactate; oleyl lactate; (iso)stearyl octanoate; isocetyloctanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetylisostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate;isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methylacetyl ricinoleate; myristyl stearate; octyl isononanoate; 2-ethylhexylisononate; octyl palmitate; octyl pelargonate; octyl stearate;octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates,ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, alkyl myristates suchas isopropyl, butyl, cetyl, 2-octyldodecyl, mirystyl, stearyl myristate,hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyllaurate, and 2-hexyldecyl laurate.

Further non-limiting mentions of esters can be made of the esters ofC₄-C₂₂ di- or tricarboxylic acids and of C₁-C₂₂ alcohols and the estersof mono-, di- or tricarboxylic acids and of C₂-C₂₆ di-, tri-, tetra- orpentahydroxy alcohols.

Even further non-limiting examples of esters include: diethyl sebacate;diisopropyl sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyladipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate;octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate;pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate;pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate;propylene glycol dicaprylate; propylene glycol dicaprate, tridecylerucate; triisopropyl citrate; triisotearyl citrate; glyceryltrilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleylcitrate, propylene glycol dioctanoate; neopentyl glycol diheptanoate;diethylene glycol diisanonate; and polyethylene glycol distearates.

Among the esters mentioned above, exemplary esters include ethyl,isopropyl, myristyl, cetyl, stearyl palmitates, ethyl-2-hexyl palmitate,2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl,cetyl, 2-octyldodecyl myristate, hexyl stearate, butyl stearate,isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurateand isononyl isononanate, cetyl octanoate.

The composition can also comprise, as fatty ester, esters and di-estersof sugars of C₆-C₃₀, such as C₁₂-C₂₂ fatty acids. “Sugar” as used in thedisclosure means oxygen-containing hydrocarbon compounds that possessseveral alcohol functions, with or without aldehyde or ketone functions,and having at least 4 carbon atoms. These sugars can be monosaccharides,oligosaccharides or polysaccharides.

As suitable sugars, non-limiting examples include sucrose, glucose,galactose, ribose, fucose, maltose, fructose, mannose, arabinose,xylose, lactose, and their derivatives, for example alkylated, such asmethylated derivatives such as methylglucose.

The esters of sugars and of fatty acids can, for example, be chosen fromthe esters or mixtures of esters of sugars described previously and oflinear or branched, saturated or unsaturated C₆-C₃₀, such as C₁₂-C₂₂fatty acids. If they are unsaturated, these compounds can have one tothree, conjugated or unconjugated, carbon-carbon double bonds.

The esters according to at least one embodiment can also be chosen frommono-, di-, tri- and tetra-esters, polyesters and mixtures thereof.

These esters can be for example oleate, laurate, palmitate, myristate,behenate, cocoate, stearate, linoleate, linolenate, caprate,arachidonates, or mixtures thereof such as the oleo-palmitate,oleo-stearate, palmito-stearate mixed esters.

For example, the mono- and di-esters can be used, and such as the mono-or di-oleate, stearate, behenate, oleopalmitate, linoleate, linolenate,oleostearate, of sucrose, of glucose or of methylglucose.

Non-limiting mention can be made of the product sold under the nameGLUCATE® DO by the company Amerchol, which is a dioleate ofmethylglucose.

Exemplary esters or of mixtures of esters of sugar of fatty acidinclude: the products sold under the names F160, F140, F110, F90, F70,SL40 by the company Crodesta, denoting respectively thepalmito-stearates of sucrose formed from 73% of monoester and 27% of di-and tri-ester, from 61% of monoester and 39% of di-, tri-, andtetra-ester, from 52% of monoester and 48% of di-, tri-, andtetra-ester, from 45% of monoester and 55% of di-, tri-, andtetra-ester, from 39% of monoester and 61% of di-, tri-, andtetra-ester, and the mono-laurate of sucrose; the products sold underthe name Ryoto Sugar Esters for example with the reference B370 andcorresponding to the behenate of sucrose formed from 20% of monoesterand 80% of di-triester-polyester; sucrose mono-di-palmito-stearatemarketed by the company Goldschmidt under the name TEGOSOFT® PSE.

The silicones usable in the composition of the present disclosureinclude but are not limited to volatile or non-volatile, cyclic, linearor branched silicones, modified or not with organic groups, having aviscosity from 5×10⁻⁶ to 2.5 m²/s at 25° C., such as from 1×10⁻⁵ to 1m²/s.

The silicones usable according to the disclosure can be in the form ofoils, waxes, resins or gums.

In some embodiments, the silicone is chosen from thepolydialkylsiloxanes, such as the polydimethylsiloxanes (PDMS), and theorgano-modified polysiloxanes having at least one functional groupselected from the poly(alkoxylated) groups, the amine groups and thealkoxy groups.

The organopolysiloxanes are defined in more detail in the work of WalterNOLL “Chemistry and Technology of Silicones” (1968), Academic Press.They can be volatile or non-volatile.

When they are volatile, the silicones are, for example, chosen fromthose with a boiling point between 60° C. and 260° C., and for furtherexamples, chosen from:

the cyclic polydialkylsiloxanes having from 3 to 7, such as from 4 to 5silicon atoms. It can be, for example, the octamethylcyclotetrasiloxanemarketed under the name VOLATILE SILICONE® 7207 by UNION CARBIDE orSILBIONE® 70045 V2 by RHODIA, the decamethylcyclopentasiloxane marketedunder the name VOLATILE SILICONE® 7158 by UNION CARBIDE, and SILBIONE®70045 V5 by RHODIA, and mixtures thereof.

Non-limiting mentions can also be made of the cyclocopolymers of thedimethylsiloxanes/methylalkylsiloxane type, such as SILICONE VOLATILE®FZ 3109 marketed by the company UNION CARBIDE, of the formula V:

Non-limiting mentions can further be made of the mixtures of cyclicpolydialkylsiloxanes with organic compounds derived from silicon, suchas the mixture of octamethylcyclotetrasiloxane andtetratrimethylsilylpentaerythritol (50/50) and the mixture ofoctamethylcyclotetrasiloxane andoxy-1,1′-(hexa-2,2,2′,2′,3,3′-trimethylsilyloxy)bis-neopentane.

Other suitable volatile silicones include the linear volatilepolydialkylsiloxanes having 2 to 9 silicon atoms and with a viscosityless than or equal to 5×10⁻⁶ m²/s at 25° C. An example isdecamethyltetrasiloxane, marketed under the name “SH 200” by the companyTORAY SILICONE. Silicones included in this class are also described inthe article published in Cosmetics and Toiletries, Vol. 91, January 76,p. 27-32-TODD BYERS “Volatile Silicone fluids for cosmetics”.

Even further non-limiting mentions can be made of non-volatilepolydialkylsiloxanes, gums and resins of polydialkylsiloxanes,polyorganosiloxanes modified with the aforementioned organofunctionalgroups, and mixtures thereof.

These silicones are, for example, chosen from the polydialkylsiloxanes,such as the polydimethylsiloxanes with trimethylsilyl end groups. Theviscosity of the silicones is measured at 25° C. according to standardASTM 445 Appendix C.

Among these polydialkylsiloxanes, mention can be made of,non-exhaustively, the following commercial products: the SILBIONE® oilsof series 47 and 70 047 or the MIRASIL® oils marketed by RHODIA, forexample the oil 70 047 V 500 000; the oils of the MIRASIL® seriesmarketed by the company RHODIA; the oils of the 200 series from thecompany DOW CORNING such as DC200, with a viscosity of 60 000 mm²/s; theVISCASIL® oils from GENERAL ELECTRIC and certain oils of the SF series(SF 96, SF 18) from GENERAL ELECTRIC.

Non-limiting mention can also be made of the polydimethylsiloxanes withdimethylsilanol end groups known under the name of dimethiconol (CTFA),such as the oils of the 48 series from the company RHODIA.

In this class of polydialkylsiloxanes, non-limiting mentions can be madeof the products marketed under the names “ABIL WAX® 9800 and 9801” bythe company GOLDSCHMIDT, which are polydialkyl(C₁-C₂₀)siloxanes.

The silicone gums usable according to the disclosure are, for example,polydialkylsiloxanes, such as polydimethylsiloxanes with highnumber-average molecular weights between 200,000 and 1,000,000 usedalone or mixed in a solvent. This solvent can be chosen from thevolatile silicones, the polydimethylsiloxane (PDMS) oils, thepolyphenylmethylsiloxane (PPMS) oils, the isoparaffins, thepolyisobutylenes, methylene chloride, pentane, dodecane, tridecane andmixtures thereof.

Products usable according to the disclosure are, for example, mixturessuch as: mixtures formed from a chain end hydroxylatedpolydimethylsiloxane, or dimethiconol (CTFA) and a cyclicpolydimethylsiloxane also called cyclomethicone (CTFA), such as theproduct Q2 1401 marketed by the company DOW CORNING; mixtures of apolydimethylsiloxane gum and a cyclic silicone such as the product SF1214 Silicone Fluid from the company GENERAL ELECTRIC, said productbeing a gum SF 30 corresponding to a dimethicone, having anumber-average molecular weight of 500,000, dissolved in the oil SF 1202Silicone Fluid corresponding to decamethylcyclopentasiloxane; mixturesof two PDMS of different viscosities, for example, of a PDMS gum and aPDMS oil, such as the product SF 1236 from the company GENERAL ELECTRIC.The product SF 1236 is a mixture of a gum SE 30 as defined above havinga viscosity of 20 m²/s and an oil SF 96 with a viscosity of 5×10⁻⁶ m²/s.This product, for example, has 15% of gum SE 30 and 85% of oil SF 96.

The organopolysiloxane resins usable according to the disclosure includebut are not limited to crosslinked siloxane systems containing theunits: R₂SiO_(2/2), R₃SiO_(1/2), RSiO_(3/2) and SiO_(4/2)

in which R represents an alkyl having 1 to 16 carbon atoms. For example,R denotes a C₁-C₄ lower alkyl group such as methyl.

Among these resins, non-limiting mention can be made of the productmarketed under the name “DOW CORNING 593” or those marketed under thenames “SILICONE FLUID SS 4230 and SS 4267” by the company GENERALELECTRIC, which are silicones of dimethyl/trimethyl siloxane structure.

Non-limiting mention can also be made of the resins of thetrimethylsiloxysilicate type, such as those marketed under the namesX22-4914, X21-5034 and X21-5037 by the company SHIN-ETSU.

The organomodified silicones usable according to the disclosure includebut are not limited to silicones as defined previously, having in theirstructure at least one organofunctional group fixed by a hydrocarbongroup.

In addition to the silicones described above, the organomodifiedsilicones can be polydiaryl siloxanes, such as polydiphenylsiloxanes,and polyalkyl-arylsiloxanes functionalized by the aforementionedorganofunctional groups.

The polyalkarylsiloxanes are, for example, chosen from thepolydimethyl/methylphenylsiloxanes, the polydimethyl/diphenylsiloxanes,linear and/or branched, with viscosity ranging from 1×10⁻⁵ to 5×10² m²/sat 25° C.

Among these polyalkarylsiloxanes, non-limiting mentins can be made ofthe products marketed under the following names: the SILBIONE® oils ofseries 70 641 from RHODIA; the oils of the series RHODORSIL® 70 633 and763 from RHODIA; the oil DOW CORNING 556 COSMETIC GRADE FLUID from DOWCORNING; the silicones of the PK series from BAYER such as the productPK20; the silicones of the series PN, PH from BAYER such as the productsPN1000 and PH1000; certain oils of the SF series from GENERAL ELECTRICsuch as SF 1023, SF 1154, SF 1250, SF 1265.

Among the organomodified silicones, non-limiting mention can be made ofthe polyorganosiloxanes having: polyoxyethylene and/or polyoxypropylenegroups optionally with C₆-C₂₄ alkyl groups such as the products calleddimethicone copolyol marketed by the company DOW CORNING under the nameDC 1248 or the oils SILWET® L 722, L 7500, L 77, L 711 from the companyUNION CARBIDE and the alkyl(C₁₂)-methicone copolyol marketed by thecompany DOW CORNING under the name Q2 5200; substituted or unsubstitutedamine groups such as the products marketed under the name GP 4 SiliconeFluid and GP 7100 by the company GENESEE or the products marketed underthe names Q2 8220 and DOW CORNING 929 or 939 by the company DOW CORNING.The substituted amine groups are, for example, C₁-C₄ aminoalkyl groups;alkoxylated groups, such as the product marketed under the name“SILICONE COPOLYMER F-755” by SWS SILICONES and ABIL WAX® 2428, 2434 and2440 by the company GOLDSCHMIDT.

For example, the fatty substance is chosen from compounds that areliquid or pasty at room temperature and at atmospheric pressure.

For further example, the fatty substance is a compound that is liquid ata temperature of 25° C. and at atmospheric pressure.

The fatty substance is, for example, chosen from the lower alkanes,fatty alcohols, esters of fatty acid, esters of fatty alcohol, and oilssuch as non-silicone mineral, vegetable and synthetic oils, includingsilicones.

According to at least one embodiment, the fatty substance is chosen fromnon-silicone compounds such as liquid paraffin, polydecenes, liquidesters of fatty acids and of fatty alcohols, and mixtures thereof.

In some embodiments, the fatty substance is chosen from alkanes,hydrocarbons and silicones.

The at least one additional fatty substance of the present invention maybe chosen from the above disclosed fatty substances other than the fattysubstance having a viscosity of greater than about 50 mm²/s at 40° C.

In certain embodiments, the at least one additional fatty substance hasa viscosity of about 50 mm²/s or less at 40° C.

A preferred additional fatty substance is mineral oil having a viscosityof about 50 mm²/s or less at 40° C., for example, ranging from betweenabout 14 to about 30 mm²/s at 40° C. and commercially available fromseveral suppliers such as Sonneborn under the tradename Blandol, Armedsaunder the tradename Aemoil M-302CG and Exxonmobil Chemical under thetradename Marcol 82.

The total amount of fatty substances, comprising the at least one fattysubstance having a viscosity of greater than about 50 mm²/s at 40° C.and optionally, the at least one additional fatty substance is at leastabout 50% by weight and may be employed in an amount ranging from about50% to about 80% by weight, preferably, from about 50% to about 70% byweight, more preferably, from about 50% to about 60% by weight, based onthe total weight of the color base composition.

In certain embodiments, the at least one fatty substance having aviscosity of greater than about 50 mm²/s at 40° C. may be employed in anamount of from about 50% to about 80% by weight, or at about 50% byweight, or at about 60% by weight, based on the total weight of thecolor base composition. When the amount of the at least one fattysubstance having a viscosity of greater than about 50 mm²/s at 40° C. isless than about 80% by weight, the at least one additional fattysubstance may be employed in an amount such that the total amount offatty substances is not more than about 80% by weight, based on thetotal weight of the color base composition.

Thus, the amount of the at least one additional fatty substance may befrom 0% to about 75% by weight, or such as from about 5% to about 70% byweight, or such as from about 5% to about 60% by weight, or such as fromabout 5% to about 50% by weight, based on the total weight of the colorbase composition.

In preferred embodiments of the present invention, the color basecomposition is in the form of a liquid emulsion or a liquid-creamemulsion.

In other embodiments of the present invention, the viscosity and/oramount of the at least one additional fatty substance are such that thecolor base composition is in the form of a liquid emulsion or aliquid-cream emulsion.

In particularly preferred embodiments of the present invention, the atleast one additional fatty substance is introduced into the color basecomposition of the present invention after an amount of the fattysubstance having a viscosity of greater than about 50 mm²/s at 40° C.has been combined with the rheology modifying polymer of the presentinvention.

The at least one fatty substance having a viscosity of greater thanabout 50 mm²/s at 40° C. and the at least one additional fatty substanceof the present invention may also be present in the oxidizingcomposition of the present invention.

Rheology Modifying Polymer

The least one rheology modifying polymer of the present invention may bechosen from a slightly alkali-swellable cross-linked acrylate polymercontained in an aqueous dispersion comprising about 30% by weight oftotal solids, a cross-linked anionic acrylate polymer contained in anaqueous dispersion comprising about 32% by weight of total solids, andmixtures thereof.

The slightly alkali-swellable cross-linked acrylate polymer contained inan aqueous dispersion comprising about 30% by weight of total solids iscommercially available from the supplier Lubrizol, under the tradenameCarbopol® Aqua SF-1 and the INCI name acrylates copolymer.

The cross-linked anionic acrylate polymer contained in an aqueousdispersion comprising about 32% by weight of total solids iscommercially available from the supplier Lubrizol, under the tradenameCarbopol® Aqua SF-2 and the INCI name acrylates crosspolymer-4.

In preferred embodiments, the at least one rheology modifying polymer ofthe present invention is neutralized in a water or an aqueous solutionwith a neutralizing agent before the polymer is added into the colorbase composition of the present invention.

In other preferred embodiments, the at least one rheology modifyingpolymer of the present invention is neutralized with a neutralizingagent at the time of addition of the polymer into the color basecomposition of the present invention.

Suitable neutralizing agents are chosen from organic amines, organicamine salts, and ammonium salts such as ethylamines, ethyleneamines,alkanolamines, cyclic amines and other cyclic compounds, saturated orunsaturated, having one or more nitrogen atoms within the ring.

The neutralizing agent is employed in an amount sufficient to neutralizethe rheology modifying polymer of the present invention in a water or anaqueous solution such that the solution becomes clear.

The at least one rheology modifying polymer of the present invention maybe employed in an amount of from about 0.3% to about 3% by weight, suchas from about 0.45% to about 2.75% by weight, further such as from about0.5% to about 2% by weight, or such as about 2.55%, or such as about1.95% by weight, based on the total weight of the color base compositionof the present invention.

In preferred embodiments, the at least one fatty substance having aviscosity of greater than about 50 mm²/s at 40° C. and the at least onerheology modifying polymer are present in the color base compositionsuch that the weight ratio of said fatty substance to the rheologymodifying polymer ranges from about 25:1 to about 3:1, or such as fromabout 22.5:1 to about 5:1, or such as from about 20:1 to about 10:1 orsuch as from about 10:1 to about 5:1.

Alkalizing Agents

The alkalizing agent of the present invention may be chosen from organicamines, organic amine salts, ammonium salts, inorganic bases, andhydroxide base compounds.

The organic amines may be chosen from the ones having a pKb at 25° C. ofless than 12, such as less than 10 or such as less than 6. It should benoted that this is the pKb corresponding to the function of highestbasicity.

Organic amines may be chosen from organic amines comprising one or twoprimary, secondary, or tertiary amine functions, and at least one linearor branched C₁-C₈ alkyl groups bearing at least one hydroxyl radical.

Organic amines may also be chosen from alkanolamines such as mono-, di-or trialkanolamines, comprising one to three identical or differentC₁-C₄ hydroxyalkyl radicals, ethylamines, ethyleneamines, quinoline,aniline and cyclic amines, such as pyrroline, pyrrole, pyrrolidine,imidazole, imidazolidine, imidazolidinine, morpholine, pyridine,piperidine, pyrimidine, piperazine, triazine and derivatives thereof.

Among the compounds of the alkanolamine type that may be mentionedinclude but not limited to: monoethanolamine (also known asmonoethanolamine or MEA), diethanolamine, triethanolamine,monoisopropanolamine, diisopropanolamine, N-dimethylaminoethanolamine,2-amino-2-methyl-1-propanol, triisopropanolamine,2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol,3-dimethylamino-1,2-propanediol, 2-amino-2-methyl-1-propanol, andtris(hydroxymethylamino)methane.

The organic amines correspond to the formula (IV):

wherein W is chosen from C₁-C₆ alkylene residues optionally substitutedwith a hydroxyl group or a C₁-C₆ alkyl radical; Rx, Ry, Rz and Rt, whichmay be identical or different, are chosen from a hydrogen atom, C₁-C₆alkyl radicals, C₁-C₆ hydroxyalkyl radicals, and C₁-C₆ aminoalkylradicals.

Examples of such amines that may be mentioned include but not limitedto: 1,3-diaminopropane, 1,3-diamino-2-propanol, spermine, andspermidine.

In some embodiments, the organic amines are chosen from amino acids.

As non-limiting examples, the amino acids that may be used may be ofnatural or synthetic origin, in L, D, or racemic form, and comprise atleast one acid function chosen from, for instance, carboxylic acid,sulfonic acid, phosphonic acid, and phosphoric acid functions. The aminoacids may be in their neutral or ionic form.

Further as non-limiting examples, the amino acids may be chosen frombasic amino acids comprising an additional amine function optionallyincluded in a ring or in a ureido function.

Such basic amino acids may be chosen from those corresponding to formula(A) below:

wherein R is a group chosen from:

The compounds corresponding to formula (A) may be chosen from histidine,lysine, arginine, ornithine, and citrulline.

Amino acids that may be used in the present disclosure include but notlimited to: aspartic acid, glutamic acid, alanine, arginine, ornithine,citrulline, asparagine, carnitine, cysteine, glutamine, glycine,histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine,proline, serine, taurine, threonine, tryptophan, tyrosine, and valine.

In some embodiments, the organic amines are chosen from basic aminoacids. The amino acids may be chosen from, for instance, arginine,lysine and histidine, or mixtures thereof.

In some embodiments, the organic amines are chosen from organic aminesof heterocyclic type. Besides histidine that has already been mentionedin the amino acids, non-limiting mention may also be made of pyridine,piperidine, imidazole, 1,2,4-triazole, tetrazole, and benzimidazole.

In some embodiments, the organic amines are chosen from amino aciddipeptides. Amino acid dipeptides that may be used in the presentdisclosure include but not limited to: carnosine, anserine, and baleine.

In some embodiments, the organic amines are chosen from compoundscomprising a guanidine function. Organic amines of this type that may beused in the present disclosure include, besides arginine that hasalready been mentioned as an amino acid, creatine, creatinine,1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine, metformin,agmatine, N-amidinoalanine, 3-guanidinopropionic acid,4-guanidinobutyric acid, and2-([amino(imino)methyl]amino)ethane-1-sulfonic acid.

As a non-limiting example, the organic amines are chosen fromalkanolamines. For example, the organic amines are chosen from2-amino-2-methyl-1-propanol and monoethanolamine, or mixtures thereof.Further as an example, the organic amine is monoethanolamine.

The alkalizing agent may be an organic amine in salt form. The term“organic amine salt,” as used herein, means organic or mineral salts ofan organic amine as described above.

As a non-limiting example, the organic salts may be chosen from thesalts of organic acids, such as citrates, lactates, glycolates,gluconates, acetates, propionates, fumarates, oxalates and tartrates.

Further as a non-limiting example, the mineral salts may be chosen fromhydrohalides (for example hydrochlorides), carbonates, hydrogencarbonates, sulfates, hydrogen phosphates, and phosphates.

The ammonium salts that may be used according to the present disclosuremay be chosen from the following acid salts: carbonate, bicarbonate. Forinstance, the salt is the carbonate, such as ammonium carbonate.

The inorganic bases that may be used may be chosen from alkali metalphosphates and carbonates such as, for example, sodium phosphate,potassium phosphate, sodium carbonate, sodium bicarbonate, potassiumcarbonate, potassium bicarbonate, and their derivatives.

The inorganic bases may also include alkali metals of carboxylates suchas, for example, sodium acetate, potassium acetate, sodium citrate, andpotassium citrate, and their derivatives.

The hydroxide base compounds can be chosen from alkali metal hydroxides,alkaline-earth metal hydroxides, transition metal hydroxides, quaternaryammonium hydroxides, organic hydroxides, and mixtures thereof. Suitableexamples are ammonium hydroxide, sodium hydroxide, potassium hydroxide,lithium hydroxide, rubidium hydroxide, caesium hydroxide, franciumhydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide,strontium hydroxide, barium hydroxide, molybdenum hydroxide, manganesehydroxide, zinc hydroxide, cobalt hydroxide, cadmium hydroxide, ceriumhydroxide, lanthanum hydroxide, actinium hydroxide, thorium hydroxide,aluminium hydroxide, guanidinium hydroxide and mixtures thereof.

According to at least one embodiment, the alkalizing agent is chosenfrom at least one organic amine such as at least one alkanolamine. Aparticularly preferred alkanolamine is ethanolamine (also known asmonoethanolamine or MEA).

The at least one alkalizing agent of the present invention may beemployed in an amount of from about 0.01% to about 30% by weight, suchas from about 0.1% to about 20% by weight, and further such as fromabout 0.5% to about 10% by weight, preferably from about 0.5% to about5%, based on the total weight of the color base composition of thepresent invention.

In certain embodiments, a portion of the alkalizing agent is used toneutralize the at least one rheology modifying polymer before or afterthe polymer is added during the process of making the color basecomposition.

According to at least one embodiment, the compositions or agents foraltering the color of keratin fibers of the present invention contain asmall amount of ammonia, or is substantially free of ammonia.

Short Chain Hydroxy Compounds

The at least one short alkyl chain hydroxy compound chosen frommonoalcohols and polyols of the present invention includes, but is notlimited to, ethanol (alcohol denatured), propanol, ethylene glycol,propylene glycol, butylene glycol, hexylene glycol, propane diol, andmixtures thereof.

Other suitable short alkyl chain hydroxy compounds chosen frommonoalcohols and polyols can be volatile or non-volatile compounds.

The at least one short alkyl chain hydroxy compound chosen frommonoalcohols and polyols may be employed according to the presentinvention in an amount ranging from about 0.5% to about 15% by weight,such as from about 1% to about 12% by weight, or such as from about 3%to about 10% by weight, or such as from about 5% to about 10% by weight,based on the total weight of the color base composition of the presentinvention.

Direct Dyes

The direct dyes useful in accordance with the present disclosure may bechosen from neutral, acidic, or cationic nitrobenzene dyes; neutral,acidic, or cationic azo direct dyes; neutral, acidic, or cationicquinone, for instance, anthraquinone, direct dyes; azine direct dyes;triarylmethane direct dyes; indoamine direct dyes; and natural directdyes.

Non-limiting examples of benzene-based direct dyes that may be usedherein include: 1,4-diamino-2-nitrobenzene,1-amino-2-nitro-4-.beta.-hydroxyethylaminobenzene,1-amino-2-nitro-4-bis(.beta.-hydroxyethyl)aminobenzene,1,4-bis(.beta.-hydroxyethylamino)-2-nitrobenzene,1-.beta.-hydroxyethylamino-2-nitro-4-bis(.beta.-hydroxyethylamino)benzene-,1-.beta.-hydroxyethylamino-2-nitro-4-aminobenzene,1-.beta.-hydroxyethylamino-2-nitro-4-(ethyl)(.beta.-hydroxyethyl)aminobenzene,1-amino-3-methyl-4-.beta.-hydroxyethylamino-6-nitrobenzene,1-amino-2-nitro-4-.beta.-hydroxyethylamino-5-chlorobenzene,1,2-diamino-4-nitrobenzene,1-amino-2-.beta.-hydroxyethylamino-5-nitrobenzene,1,2-bis(.beta.-hydroxyethylamino)-4-nitrobenzene,1-amino-2-tris(hydroxymethyl)methylamino-5-nitrobenzene,1-hydroxy-2-amino-5-nitrobenzene, 1-hydroxy-2-amino-4-nitrobenzene,1-hydroxy-3-nitro-4-aminobenzene,1-.beta.-hydroxyethyloxy-2-.beta.-hydroxyethylamino-5-nitrobenzene,1-methoxy-2-.beta.-hydroxyethylamino-5-nitrobenzene,1-.beta.-hydroxyethyloxy-3-methylamino-4-nitrobenzene,1-.beta.,.gamma.-dihydroxypropyloxy-3-methylamino-4-nitrobenzene,1-.beta.-hydroxyethylamino-4-.beta.,.gamma.-dihydroxypropyloxy-2-nitrobenzene,1-.beta.,.gamma.-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene,1-.beta.-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene,1-.beta.-hydroxyethylamino-3-methyl-2-nitrobenzene,1-.beta.-aminoethylamino-5-methoxy-2-nitrobenzene,1-hydroxy-2-chloro-6-ethylamino-4-nitrobenzene,1-hydroxy-2-chloro-6-amino-4-nitrobenzene,1-hydroxy-6-bis(.beta.-hydroxyethyl)amino-3-nitrobenzene,1-.beta.-hydroxyethylamino-2-nitrobenzene, and1-hydroxy-4-.beta.-hydroxyethylamino-3-nitrobenzene.

Suitable azo direct dyes may be chosen from, but not limited to, thecationic azo dyes described in International Patent ApplicationPublication Nos. WO 95/15144, WO 95/01772, WO 02/078 660, WO 02/100 834,and WO 02/100 369, European Patent Application No. 0 714 954, and FrenchPatent Application Nos. 2 822 696, 2 825 702, 2 825 625, 2 822 698, 2822 693, 2 822 694, 2 829 926, 2 807 650, and 2 844 269, which areincorporated herein by reference in their entireties.

Examples of such azo compounds include, but are not limited to:1,3-dimethyl-2-[[4-(dimethylamino)phenyl]azo]-1H-imidazolium chloride,1,3-dimethyl-2-[(4-aminophenyl)azo]-1H-imidazolium chloride, and1-methyl-4-[(methylphenylhydrazono)methyl]pyridinium methyl sulfate.

Further non-limiting examples of suitable azo direct dyes include thefollowing dyes, described in the Color Index International, 3rd edition:Acid Yellow 9, Acid Black 1, Basic Red 22, Basic Red 76, Basic Yellow57, Basic Brown 16, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red35, Basic Brown 17, Acid Yellow 23, and Acid Orange 24.

1-(4′-aminodiphenylazo)-2-methyl-4-bis(.beta.-hydroxyethyl)aminobenzeneand 4-hydroxy-3-(2-methoxyphenylazo)-1-naphthalenesulfonic acid are alsosuitable for use as azo direct dyes.

Quinone direct dyes may be chosen, for example, from: Acid Violet 43,Acid Blue 62, Basic Blue 22, Basic Blue 99, and also1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone,1-aminopropylamino-4-methylaminoanthraquinone,1-aminopropylaminoanthraquinone,5-.beta.-hydroxyethyl-1,4-diaminoanthraquinone,2-aminoethylaminoanthraquinone, and1,4-bis(.beta.,.gamma.-dihydroxypropylamino)anthraquinone.

Non-limiting examples of azine dyes include: Basic Blue 17, and BasicRed 2.

Suitable triarylmethane dyes may include, for example: Basic Green 1,Acid blue 9, Basic Violet 3, Basic Violet 14, Basic Blue 7, Acid Violet49, Basic Blue 26, and Acid Blue 7.

A non-limiting example of an indoamine dye that may be used inaccordance with the present disclosure is:2-.beta.-hydroxyethylamino-5-[bis(.beta.-4′-hydroxyethyl)amino]anilino-1,-4-benzoquinone.

Natural direct dyes may be chosen, for example, from carminic acid,kermesic acid, purpurogallin, protocatechualdehyde, isatin, curcumin,spinulosin, and apigenidin. It is also possible to use extracts ordecoctions containing these natural dyes, for example, henna-basedpoultices and extracts.

The at least one direct dye may be present in the dye composition in anamount ranging from 0.001% to 20% by weight relative to the total weightof the dye composition, for example, from 0.005% to 10% by weight.

Oxidative Dye Precursors

Typically the oxidative dye precursors are selected from ortho- orpara-phenylenediamines, ortho- or para-aminophenols and heterocycliccompounds. These oxidation bases are colourless or lightly colouredcompounds which, in combination with oxidizing products, allow colouredspecies to be obtained, by a process of oxidative condensation.

Useful oxidative dye precursors of the present disclosure include, byway of example only, aromatic diamines, polyhydric phenols, aminophenols, and derivatives of these compounds, such as, for example,N-substituted derivatives of the amines, and ethers of the phenols.

By way of non-limiting example, oxidative dye precursors may be chosenfrom ortho- or para-aminophenols, ortho- or para-phenylenediamines,double bases, heterocyclic bases, and the acid addition salts thereof.

Exemplary para-phenylenediamines which may be chosen include compoundsof the general formula (IV) and their addition salts with an acid:

wherein, in formula (IV):

-   -   R8 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4        monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a        (C1-C4)alkoxy(C1-C4)alkyl radical, a C1-C4 alkyl radical        substituted by a nitrogenous group, a phenyl radical or a        4′-aminophenyl radical;    -   R9 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4        monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a        (C1-C4)alkoxy(C1-C4)alkyl radical or a C1-C4 radical substituted        by a nitrogenous group;    -   R8 and R9 can also form, with the nitrogen atom which carries        them, a 5- or 6-membered nitrogenous heterocycle optionally        substituted by one or more alkyl, hydroxyl or ureido groups;    -   R10 represents a hydrogen atom, a halogen atom, such as a        chlorine atom, a C1-C4 alkyl radical, a sulpho radical, a        carboxyl radical, a C1-C4 monohydroxyalkyl radical, a C1-C4        hydroxyalkoxy radical, a C1-C4 acetylaminoalkoxy radical, a        C1-C4 mesylaminoalkoxy radical or C1-C4 carbamoylaminoalkoxy        radicals; and    -   R11 represents a hydrogen atom, a halogen atom or a C1-C4 alkyl        radical.

By way of example, among the nitrogenous groups in the above formula(IV), of the amino, mono(C1-C4)alkylamino, di(C1-C4)alkylamino,tri(C1-C4)alkylamino, monohydroxy(C1-C4)alkylamino, imidazolinium andammonium radicals may be chosen. Exemplary para-phenylenediamines ofabove formula (XXIII), include para-phenylenediamine,para-toluylenediamine, 2-chloro-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine,2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine,N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine,N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline,N,N-bis(beta-hydroxyethyl)-para-phenylenediamine,4-N,N-bis(beta-hydroxyethyl)amino-2-methylaniline,4-N,N-bis(beta-hydroxyethyl)amino-2-chloroaniline,2-(beta-hydroxyethyl)-para-phenylenediamine,2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine,N-(beta-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-beta-methyl-para-phenylenediamine,N-ethyl-N-(beta-hydroxyethyl)-para-phenylenediamine,N-(beta,gamma-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine,2-((beta-hydroxyethyloxy)-para-phenylenediamine,2-((beta-acetylaminoethyloxy)-para-phenylenediamine,N-(beta-methoxyethyl)-para-phenylenediamine,2-methyl-1-N-(beta-hydroxyethyl)-para-phenylenediamine and theiraddition salts with an acid.

Exemplary ortho-phenylenediamines, includeN1-(2-hydroxyethyl)-4-nitro-o-phenylenediamine,4-methyl-o-phenylenediamine, and 4-nitro-o-phenylenediamine and acidaddition salts thereof.

As used herein, the term “double bases” means compounds comprising atleast two aromatic nuclei having at least one of amino and hydroxylgroups. For example, double bases may be chosen from compounds of theformula (V) and their addition salts with an acid:

wherein, in formula (V):

-   -   Z1 and Z2 may independently be chosen from a hydroxyl or —NH2        radical which can be substituted by a C1-C4 alkyl radical or by        a connecting arm Y;    -   the connecting arm Y is chosen from a linear or branched        alkylene chain comprising from 1 to 14 carbon atoms which can be        interrupted or terminated by one or more nitrogenous groups        and/or by one or more heteroatoms, such as oxygen, sulphur or        nitrogen atoms, and which is optionally substituted by one or        more hydroxyl or C1-C6 alkoxy radicals;    -   R12 and R13 are independently chosen from a hydrogen or halogen        atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a        C2-C4 polyhydroxyalkyl radical, a C1-C4 aminoalkyl radical or a        connecting arm Y;    -   R14, R15, R16, R17, R18 and R19 are independently chosen from a        hydrogen atom, a connecting arm Y or a C1-C4 alkyl radical;

wherein compounds of formula (V) only comprise a single connecting arm Yper molecule.

In various embodiments, nitrogenous groups of the above formula (V), maybe chosen from amino, mono(C1-C4)alkylamino, di(C1-C4)alkylamino,tri(C1-C4)alkylamino, monohydroxy(C1-C4)alkylamino, imidazolinium andammonium radicals.

Nonlimiting examples of double bases includeN,N′-bis(beta-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diamino-propan-ol,N,N′-bis(beta-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(beta-aminophenyl)-tetramethylenediamine,N,N′-bis(4-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-diethyl-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine,1,8-bis(2,5-diamino-phenoxy)-3,5-dioxaoctane, and their addition saltswith an acid.

Non-limiting examples of para-aminophenols which can be used in thecontext of the invention can be chosen in particular from the compoundscorresponding to the following formula (VI): and their addition saltswith an acid:

wherein, in formula (VI):

-   -   R20 is chosen from a hydrogen atom, a halogen atom, such as        fluorine, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl        radical, a (C1-C4)alkoxy(C1-C4)alkyl radical, a C1-C4 aminoalkyl        radical or a hydroxy(C1-C4)alkylamino-(C1-C4)alkyl radical, and    -   R21 is chosen from a hydrogen atom, a halogen atom, such as        fluorine, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl        radical, a C2-C4 polyhydroxyalkyl radical, a C1-C4 aminoalkyl        radical, a C1-C4 cyanoalkyl radical or a        (C1-C4)alkoxy(C1-C4)alkyl radical.

By way of example only, para-aminophenol, 4-amino-3-methylphenol,4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethyl phenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(beta-hydroxyethylaminomethyl)phenol,N-methyl-para-aminophenol, and the acid addition salts thereof may bechosen.

Exemplary ortho-aminophenols may be chosen from 2-aminophenol,2-amino-1-hydroxy-5-methylbenzene, 2-amino-1-hydroxy-6-methylbenzene,5-acetamido-2-aminophenol, and the acid addition salts thereof.

Exemplary heterocyclic bases may be chosen from pyridine derivatives,pyrimidine derivatives, pyrazole derivatives, pyrazolinone derivatives,and the acid addition salts thereof.

Non-limiting examples of pyridine derivatives include, for example,those disclosed in GB1026978 and GB1153196, both incorporated byreference herein, such as 2,5-diaminopyridine,2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine,2-(beta-methoxyethyl)amino-3-amino-6 methoxypyridine,3,4-diaminopyridine, and the acid addition salts thereof.

Non-limiting examples of pyrimidine derivatives include, for example,those described in DE 2 359 399, JP 88-169 571, JP 91-10659 and WO96/15765, all incorporated by reference herein, such as2,4,5,6-tetra-aminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,2-hydroxy-4,5,6-triamino-pyrimidine,2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and thepyrazolopyrimidine derivatives, such as those mentioned in FrenchApplication FR-A-2 750 048 and among which may be mentionedpyrazolo[1,5-a]pyrimidine-3,7-diamine;2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;pyrazolo[1,5-a]pyrimidine-3,5-diamine;2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine;3-aminopyrazolo[1,5-a]pyrimidin-7-ol;3-aminopyrazolo[1,5-a]pyrimidin-5-ol;2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol;2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol;2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)(2-hydroxyethyl)amino]ethanol;2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)(2-hydroxyethyl)amino]ethanol;5,6-dimethyl-pyrazolo[1,5-a]pyrimidine-3,7-diamine;2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;3-amino-5-methyl-7-(imidazolylpropylamino)pyrazolo[1,5-a]pyrimidine; andtheir addition salts and their tautomeric forms, when there exists atautomeric equilibrium, and their addition salts with an acid.

Non-limiting examples of pyrazole and pyrazolinone derivatives includethe compounds described in DE 3,843,892, DE 4,133,957, WO 94/08969, WO94/08970, FR-A-2,733,749, and DE 195 43 988, all of which areincorporated by reference herein, such as 4,5-diamino-1-methyl-pyrazole,3,4-diaminopyrazole, 4,5-diamino-1-(4′-chlorobenzyl)pyrazole,4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole,4,5-diamino-1-methyl-3-phenylpyrazole,4-amino-1,3-dimethyl-5-hydrazinopyrazole,1-benzyl-4,5-diamino-3-methylpyrazole,4,5-diamino-3-tert-butyl-1-methylpyrazole,4,5-diamino-1-tert-butyl-3-methylpyrazole,4,5-diamino-1-(beta-hydroxyethyl)-3-methylpyrazole,4,5-diamino-1-(beta-hydroxyethyl)pyrazole,4,5-diamino-1-ethyl-3-methylpyrazole,4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole,4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,4,5-diamino-3-hydroxymethyl-1-methylpyrazole,4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,4,5-diamino-3-methyl-1-isopropylpyrazole,4-amino-5-(2′-aminoethyl)amino-1,3-dimethyl-pyrazole,3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole,3,5-diamino-1-methyl-4-methylaminopyrazole,3,5-diamino-4-(p-hydroxyethyl)amino-1-methylpyrazole,2-(4,5-diamino-1H-pyrazol-1-yl), H2SO4,2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-z]pyrazol-1-one,1-methyl-3-phenyl-2-pyrazolinone, and the acid addition salts thereof.

The at least one oxidation dye precursor may be present in the colorbase composition of the present disclosure in an amount ranging from,for example, about 0.0001% to about 12%, such as from about 0.0001% toabout 8.0%, or from about 0.005% to about 5% by weight, based on thetotal weight of the color base composition.

Furthermore, one or more oxidative dye precursors of the presentdisclosure may be employed in combination with one or more couplers.

The shades obtained with the use of oxidative dye precursors are veryoften varied by combining them with one or more couplers, the latterbeing selected in particular from aromatic meta-diamines,meta-aminophenols, meta-diphenols and certain heterocyclic compounds,such as indole compounds.

The variety of the molecules employed for the oxidation bases andcouplers allows a rich palette of colours to be obtained.

The couplers that may be used in the present disclosure include thoseconventionally used in oxidative methods of coloring keratinous fibers,for example, meta-aminophenols, meta-phenylenediamines andmeta-diphenols, naphthols, mono- or polyhydroxylated naphthalenederivatives, and heterocyclic couplers such as, for example, indolederivatives, indoline derivatives, sesamol and its derivatives, pyridinederivatives, pyrazolotriazole derivatives, pyrazolones, indazoles,benzimidazoles, benzothiazoles, benzoxazoles, 1,3-benzodioxoles,quinolines, benzomorpholine derivatives, pyrazoloazole derivatives,pyrroloazole derivatives, imidazoloazole derivatives, pyrazolopyrimidinederivatives, pyrazoline-3,5-dione derivatives, pyrrolo[3,2-d]oxazolederivatives, pyrazolo[3,4-d]thiazole derivatives, thiazoloazole S-oxidederivatives, thiazoloazole S,S-dioxide derivatives, and the acidaddition salts thereof.

Suitable color couplers include, for example, those having the generalformula (D):

wherein R₁ is unsubstituted hydroxy or amino, or hydroxy or aminosubstituted with one or more C₁₋₆ hydroxyalkyl groups, R₃ and R₅ areeach independently hydrogen, hydroxy, amino, or amino substituted withC₁₋₆ alkyl, C₁₋₆ alkoxy, or C₁₋₆ hydroxyalkyl group; and R₂, R₄, and R₆are each independently hydrogen, C₁₋₆ alkoxy, C₁₋₆ hydroxyalkyl, or C₁₋₆alkyl, or R₃ and R₄ together may form a methylenedioxy or ethylenedioxygroup. Examples of such compounds include meta-derivatives such asphenols, meta-aminophenols, meta-phenylenediamines, and the like, whichmay be unsubstituted, or substituted on the amino group or benzene ringwith alkyl, hydroxyalkyl, alkylamino groups, and the like. Suitablecouplers include m-aminophenol, 2,4-diaminotoluene, 4-amino,2-hydroxytoluene, phenyl methyl pyrazolone, 3,4-methylenedioxyphenol,3,4-methylenedioxy-1-[(β-hydroxyethyl)amino]benzene,1-methoxy-2-amino-4-[(β-hydroxyethyl)amino]benzene,1-hydroxy-3-(dimethylamino)benzene,6-methyl-1-hydroxy-3[(β-hydroxyethyl)amino]benzene,2,4-dichloro-1-hydroxy-3-aminobenzene,1-hydroxy-3-(diethylamino)benzene, 1-hydroxy-2-methyl-3-aminobenzene,2-chloro-6-methyl-1-hydroxy-3-aminobenzene, 1,3-diaminobenzene,6-methoxy-1,3-diaminobenzene, 6-hydroxyethoxy-1,3-diaminobenzene,6-methoxy-5-ethyl-1,3-diaminobenzene, 6-ethoxy-1,3-diaminobenzene,1-bis(β-hydroxyethyl)amino-3-aminobenzene, 2-methyl-1,3-diaminobenzene,6-methoxy-1-amino-3-[(β-hydroxyethyl)amino]-benzene,6-(β-aminoethoxy)-1,3-diaminobenzene,6-(β-hydroxyethoxy)-1-amino-3-(methylamino)benzene,6-carboxymethoxy-1,3-diaminobenzene,6-ethoxy-1-bis(β-hydroxyethyl)amino-3-aminobenzene,6-hydroxyethyl-1,3-diaminobenzene,1-hydroxy-2-isopropyl-5-methylbenzene, 1,3-dihydroxybenzene,2-chloro-1,3-dihydroxybenzene, 2-methyl-1,3-dihydroxybenzene,4-chloro-1,3-dihydroxybenzene,5,6-dichloro-2-methyl-1,3-dihydroxybenzene, 1-hydroxy-3-amino-benzene,1-hydroxy-3-(carbamoylmethylamino)benzene, 6-hydroxybenzomorpholine,4-methyl-2,6-dihydroxypyridine, 2,6-dihydroxypyridine,2,6-diaminopyridine, 6-aminobenzomorpholine,1-phenyl-3-methyl-5-pyrazolone, 1-hydroxynaphthalene,1,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 5-amino-2-methylphenol, 4-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindole,6-hydroxyindoline, 2,4-diamionphenoxyethanol, and mixtures thereof.

Other couplers may be chosen, for example, from2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-methyl-5-aminophenol,5-N-(β-hydroxyethyl)amino-2-methylphenol, 3-aminophenol,1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,4-chloro-1,3-dihydroxybenzene, 2,4-diamino 1-(β-hydroxyethyloxy)benzene,2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene,1,3-bis(2,4-diaminophenoxy)propane, sesamol,1-amino-2-methoxy-4,5-methylenedioxybenzene, α-naphthol,6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole,6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine,1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one,2-amino-3-hydroxypyridine, 3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazole,2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,6-methylpyrazolo[1,5-a]-benzimidazole, and the acid addition saltsthereof.

In one embodiment, the couplers include resorcinol, 1-naphthol,2-methylresorcinol, 4-amino-2-hydroxy toluene, m-aminophenol,2,4-diaminophenoxyethanol, phenyl methylpyrazolone,hydroxybenzomorpholine, 2-methyl-5-hydroxyethylaminophenol,6-hydroxyindole, 2-amino-3-hydroxypyridine, 5-amino-6-chloro-o-cresol,4-chlororesorcinol, their salts, and mixtures thereof.

When they are present, couplers may be present in amounts ranging fromabout 0.0001% to about 12% by weight; or from about 0.1% to about 8% byweight; or from about 1% to about 5% based on the total weight of thecolor base composition.

In general, the acid addition salts of the oxidation bases and couplersmay be chosen from hydrochlorides, hydrobromides, sulphates, tartrates,lactates, and acetates.

Oxidizing Agent

When oxidative dye precursors are present in the color basecompositions, the agent for altering the color of keratin fibers of thepresent invention requires an oxidizing composition including at leastone oxidizing agent which may be chosen, for example, from a peroxide, apersulfate, a perborate, a percarbonate, alkali metal bromates,ferricyanides or a mixture thereof. Oxidizing agents that may also beused include at least one redox enzyme such as laccases, peroxidases,and 2-electron oxidoreductases, such as uricase, where appropriate inthe presence of their respective donor or co-factor. Oxygen in the airmay also be employed as an oxidizing agent.

In one embodiment, the oxidizing agent is hydrogen peroxide present inan aqueous solution whose titre may range from 1 to 40 volumes, such asfrom 5 to 40 volumes or such as from 5 to 20 volumes.

In another embodiment, the oxidizing agent is a persulfate and/or amonopersulfate such as, for example, potassium persulfate, sodiumpersulfate, ammonium persulfate, as well as mixtures thereof. In oneembodiment the oxidizing agents in the present disclosure are selectedfrom hydrogen peroxide, potassium persulfate, sodium persulfate andmixtures thereof.

In general, the oxidizing agent will be present in an amount of fromabout 0.05 to about 50% by weight, such as from about 0.1% to about 30%by weight, or such as from about 0.1% to about 20% by weight, or such asfrom about 1% to about 12% by weight, based on the total weight of theoxidizing composition.

Cosmetically Acceptable Medium

The compositions of the present invention can comprise other compoundsconstituting the cosmetically acceptable medium. This cosmeticallyacceptable medium comprises water or a mixture of water and at least onecosmetically acceptable organic solvent.

As examples of organic solvents, non-limiting mentions can be made ofalcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol, andphenylethyl alcohol, or glycols or glycol ethers such as, for example,monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propyleneglycol or ethers thereof such as, for example, monomethyl ether ofpropylene glycol, butylene glycol, hexylene glycol, dipropylene glycolas well as alkyl ethers of diethylene glycol, for example monoethylether or monobutyl ether of diethylene glycol.

pH

The pH of the color base composition is greater than 7 and may rangefrom about 7.1 to about 14, or such as from about 7.5 to about 11, orsuch as from about 7.5 to about 10 or such as from about 7.5 to about 9,or such as from about 9 to about 11, and it may be adjusted to thedesired value using acidifying or basifying agents that are well knownin the art in the dyeing of keratin fibers.

The pH of the agent for altering the color of keratin fibers, i.e., thecomposition resulting from mixing together the color base compositionand the oxidizing composition, may range from about 2 to about 14, suchas from about 3 to about 13, or such as from about 4 to about 11.

In certain embodiments, the pH of the agent for altering the color ofkeratin fibers may be below 7, such as from about 2 to 6.8, or, may beabove 7, such as from about 7.1 to about 12, or such as from about 7.1to about 11, or such as from about 7.5 to about 10.

The color base composition of the present disclosure is preferably inthe form of an emulsion, for example, oil-in-water emulsion andwater-in-oil emulsion.

In particularly preferred embodiments, the color base composition of thepresent disclosure is preferably in the form of an oil-in-wateremulsion.

The color base and the oxidizing compositions of the present inventionmay further comprise at least one auxiliary agent. The auxiliary agentmay include, but is not limited to thickening agents and rheologymodifying polymers other than those described above (such as thosecommercially available as Carbopol® Aqua SF-1 and Carbopol® Aqua SF-2),cationic polymers, film forming polymers, pigments, dyes, humectants andmoisturizing agents, emulsifying agents other than those that fall underthe above-described fatty substances, structuring agents, propellants,surfactants, shine agents, and conditioning agents.

Thickening agents and rheology modifying polymers other than theabove-described rheology modifying polymers (such as those commerciallyavailable as Carbopol® Aqua SF-1 and Carbopol® Aqua SF-2) may furthercomprise the compositions of the present invention and may be chosenfrom polymeric thickeners and non-polymeric thickeners as described inUS2010154140A, herein incorporated by reference in its entirety.

Thickening agents of the present invention may be chosen from polymericthickeners and non-polymeric thickeners. The at least one polymericthickener can be chosen from ionic or non-ionic, associative ornon-associative polymers. Exemplary polymeric thickeners include variousnative gums. Representative non-polymeric thickening agents includemineral salts such as sodium chloride; oxyethylenated molecules andespecially ethoxylated alkyl or acyl derivatives of polyols. Thesepolymers can be modified physically or chemically.

The at least one thickening agent of the present invention is preferablyused in an amount of from greater than 0% to about 15% by weight,preferably from about 0.1% to about 10% by weight, and more preferablyfrom about 1% to about 5% by weight, based on the total weight of thecolor base or oxidizing composition of the present invention.

The color base and oxidizing compositions according to the presentinvention can also comprise at least one cationic polymer.

In at least one embodiment, the at least one cationic polymer includedin the compositions of the disclosure is not chosen from cationicassociative polymers. In other words, these cationic polymers do notcomprise in their structure a pendent or terminal hydrophobic chain, forexample of alkyl or alkenyl type, containing from 10 to 30 carbon atoms.

The at least one cationic polymer of the compositions according to thedisclosure can be chosen from, for example:

(1) homopolymers and copolymers derived from acrylic or methacrylicesters or amides and comprising at least one unit chosen from units offormulae (VI), (VII), (VIII) and (IX):

wherein:

R₃, which may be identical or different, denotes a hydrogen atom or aCH₃ radical;

A, which may be identical or different, represents a linear or branchedC₁-C₆ and, for example, C₂-C₃ alkyl group or a C₁-C₄ hydroxyalkyl group;

R₄, R₅ and R₆, which may be identical or different, represent a C₁-C₁₈alkyl group or a benzyl radical, such as a C₁-C₆ alkyl group;

R₁ and R₂, which may be identical or different, represent hydrogen or aC₁-C₆ alkyl group, for example methyl or ethyl;

X⁻ denotes an anion derived from a mineral or organic acid, such as amethosulfate anion or a halide such as chloride or bromide.

The polymers of this family can also contain at least one unit derivedfrom at least one comonomer which may be chosen from the family ofacrylamides, methacrylamides, diacetone acrylamides, acrylamides andmethacrylamides substituted on the nitrogen with lower (C₁-C₄)alkyls,acrylic or methacrylic acids or esters thereof, vinyllactams such asvinylpyrrolidone or vinylcaprolactam, and vinyl esters.

Thus, among the polymers of this family, exemplary mention may be madeof:

copolymers of acrylamide and of dimethylaminoethyl acrylate quaternizedwith dimethyl sulfate or with a dimethyl halide, such as the productsold under the name HERCOFLOC by the company Hercules,

the copolymers of acrylamide and ofmethacryloyloxyethyltrimethylammonium chloride described, for example,in EP 80 976 and sold under the name BINA QUAT P 100 by the company CibaGeigy,

the copolymer of acrylamide and of methacryloyloxyethyltrimethylammoniummethosulfate sold under the name RETEN by the company Hercules,

quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkylacrylate or acrylate copolymers, such as the products sold under thename GAFQUAT by the company ISP, for instance GAFQUAT 734 or GAFQUAT755, or alternatively the products known as COPOLYMER 845, 958 and 937,

dimethylaminoethyl acrylate/vinylcaprolactam/vinylpyrrolidoneterpolymers, such as the product sold under the name GAFFIX VC 713 bythe company ISP,

vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers sold, forexample, under the name STYLEZE CC 10 by ISP, quaternizedvinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers such asthe product sold under the name GAFQUAT HS 100 by the company ISP, andcrosslinked polymers ofmethacryloyloxy(C₁-C₄)alkyltri(C₁-C₄)alkylammonium salts such as thepolymers obtained by homopolymerization of dimethylaminoethyl acrylatequaternized with methyl chloride, or by copolymerization of acrylamidewith dimethylaminoethyl acrylate quaternized with methyl chloride, thehomo- or copolymerization being followed by crosslinking with a compoundcontaining olefinic unsaturation, such as methylenebisacrylamide. In atleast one embodiment, a crosslinkedacrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer(20/80 by weight) in the form of a dispersion containing 50% by weightof the copolymer in mineral oil can be used. This dispersion is soldunder the name SALCARE® SC 92 by the company Ciba. In some embodiments,a crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymercontaining about 50% by weight of the homopolymer in mineral oil or in aliquid ester can be used. These dispersions are sold under the namesSALCARE® SC 95 and SALCARE® SC 96 by the company Ciba.

Other examples are cellulose ether derivatives comprising quaternaryammonium groups, such as the polymers sold under the names JR (JR 400,JR 125, JR 30M) or LR (LR 400, LR 30M) by the company Union CarbideCorporation.

(2) copolymers of cellulose or cellulose derivatives grafted with awater-soluble quaternary ammonium monomer, such as hydroxymethyl-,hydroxyethyl- or hydroxy-propylcelluloses grafted, for instance, with amethacryloylethyltrimethylammonium,methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.These are sold under the name CELQUAT L 200 and CELQUAT H 100 by thecompany National Starch.

(3) non-cellulose cationic polysaccharides, such as guar gums containingtrialkylammonium cationic groups. Such products are sold, for example,under the trade names JAGUAR C13S, JAGUAR C15, JAGUAR C17 and JAGUARC162 by the company Meyhall.

(4) polymers of piperazinyl units and of divalent alkylene orhydroxyalkylene radicals.

(5) water-soluble polyamino amides prepared, for example, bypolycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked with an epihalohydrin, a diepoxide, adianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, abis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkylhalide or alternatively with an oligomer resulting from the reaction ofa difunctional compound which is reactive with a bis-halohydrin, abis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, anepihalohydrin, a diepoxide or a bis-unsaturated derivative; thecrosslinking agent being used in an amount ranging from 0.025 to 0.35mol per amine group of the polyamino amide; these polyamino amides canbe alkylated or, if they contain at least one tertiary amine function,they can be quaternized. Exemplary mention may be made of the adipicacid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold underthe name CARTARETINE F, F4 or F8 by the company Sandoz.

(6) the polymers obtained by reaction of at least one polyalkylenepolyamine containing two primary amine groups and at least one secondaryamine group with a dicarboxylic acid chosen from diglycolic acid andsaturated C₃-C₈ aliphatic dicarboxylic acids. The molar ratio betweenthe polyalkylene polyamine and the dicarboxylic acid ranges from 0.8:1to 1.4:1; the polyamino amide resulting therefrom is reacted withepichlorohydrin in a molar ratio of epichlorohydrin relative to thesecondary amine group of the polyamino amide ranging from 0.5:1 to1.8:1. Polymers of this type are sold, for example, under the nameHERCOSETT 57, PD 170 or DELSETTE 101 by the company Hercules.

(7) cyclopolymers of alkyldiallylamine and of dialkyldiallylammonium,such as the homopolymers or copolymers containing, as main constituentof the chain, at least one unit corresponding to formula (X) or (XI):

wherein formulae k and t are equal to 0 or 1, the sum k+t being equal to1; R₉ denotes a hydrogen atom or a methyl radical; R₇ and R₈,independently of each other, denote a C₁-C₈ alkyl group, a hydroxyalkylgroup in which the alkyl group is C₁-C₅, an amidoalkyl group in whichthe alkyl is C₁-C₄; or R₇ and R₈ denote, together with the nitrogen atomto which they are attached, a heterocyclic group such as piperidyl ormorpholinyl; in at least one embodiment R₇ and R₈, independently of eachother, denote a C₁-C₄ alkyl group; Y⁻ is an organic or mineral anionsuch as bromide, chloride, acetate, borate, citrate, tartrate,bisulfate, bisulfite, sulfate or phosphate.

Among the polymers defined above, exemplary mention may be made of thedimethyldiallylammonium chloride homopolymer sold under the nameMERQUAT® 100 and MERQUAT® 280 by the company Nalco (and its homologuesof low weight-average molecular mass) and the copolymers ofdiallyldimethylammonium chloride and of acrylamide, sold under the nameMERQUAT® 550.

(8) quaternary diammonium polymers containing repeating units of formula(XII):

wherein:

R₁₀, R₁₁, R₁₂ and R₁₃, which may be identical or different, representC₁-C₆ aliphatic, alicyclic or arylaliphatic radicals orhydroxyalkylaliphatic radicals wherein the alkyl radical is C₁-C₄, oralternatively R₁₀, R₁₁, R₁₂ and R₁₃, together or separately, constitute,with the nitrogen atoms to which they are attached, heterocyclesoptionally containing a second heteroatom other than nitrogen, oralternatively R₁₀, R₁₁, R₁₂ and R₁₃ represent a linear or branched C₁-C₆alkyl radical substituted with a nitrile, ester, acyl or amide group ora group —CO—O—R₁₄-D or —CO—NH—R₁₄-D wherein R₁₄ is an alkylene and D isa quaternary ammonium group;

A₁ and B₁ represent C₂-C₆ polymethylene groups which are linear orbranched, saturated or unsaturated, and which optionally contain, linkedto or intercalated in the main chain, at least one aromatic ring or atleast one atom chosen from oxygen and sulfur atom or at least one groupchosen from sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl,quaternary ammonium, ureido, amide and ester groups, and

X⁻ denotes an anion derived from a mineral or organic acid;

A₁, R₁₀ and R₁₂ can form, with the two nitrogen atoms to which they areattached, a piperazine ring;

and wherein, if A₁ denotes a linear or branched, saturated orunsaturated alkylene or hydroxyalkylene radical, B₁ can also denote agroup —(CH₂)_(n)—CO-D-OC—(CH₂)_(n)— wherein n is a number ranging from 1to 6, and D is chosen from:

a) a glycol residue of formula: —O—Z—O—, where Z denotes a linear orbranched hydrocarbon-based radical or a group corresponding to one ofthe following formulae: —(CH₂—CH₂—O)_(x)—CH₂—CH₂—; or—[CH₂—CH(CH₃)—O]_(y)—CH₂—CH(CH₃)—, where x and y denote an integerranging from 1 to 4, representing a defined and unique degree ofpolymerization or any number ranging from 1 to 4 representing an averagedegree of polymerization;

b) a bis-secondary diamine residue such as a piperazine derivative;

c) a bis-primary diamine residue of formula: —NH—Y—NH—, wherein Ydenotes a linear or branched hydrocarbon-based radical, or alternativelythe radical —CH₂—CH₂—S—S—CH₂—CH₂—; and

d) a ureylene group of formula: —NH—CO—NH—.

In at least one embodiment, X⁻ is an anion such as chloride or bromide.

These polymers, for example, have a number-average molecular massranging from 1000 to 100,000.

In some embodiments, polymers are used that consist of repeating unitscorresponding to formula (XIII):

wherein R₁₀, R₁₁, R₁₂ and R₁₃, which may be identical or different,denote a C₁-C₄ alkyl or hydroxyalkyl radical, n and p are integersranging from 2 to 6, and X⁻ is an anion derived from a mineral ororganic acid.

In at least one embodiment, the at least one cationic polymercorresponding to this family comprise repeating units of formulae (W)and (U):

for example those whose molecular weight, determined by gel permeationchromatography, ranges from 9,500 to 9,900;

for instance those whose molecular weight, determined by gel permeationchromatography, is 1200.

(9) polyquaternary ammonium polymers consisting of repeating units offormula (XIV):

wherein p denotes an integer ranging from 1 to 6, D may be zero or mayrepresent a group —(CH₂)_(r)—CO— wherein r denotes a number ranging from1 to 6, and X⁻ is an anion.

Such polymers may be prepared according to the processes described inU.S. Pat. Nos. 4,157,388, 4,702,906 and 4,719,282. They are described,for example, in patent application EP 122 324.

Among these polymers, examples that may be mentioned include theproducts MIRAPOL A 15, MIRAPOL AD1, MIRAPOL AZ1 and MIRAPOL 175 sold bythe company Miranol.

(10) quaternary polymers of vinylpyrrolidone and of vinylimidazole, forinstance the products sold under the names LUVIQUAT FC 905, FC 550 andFC 370 by the company BASF.

(11) vinylamide homopolymers or copolymers, such as partially hydrolysedvinylamide homopolymers such as poly(vinylamine/vinylamide)s.

(12) cationic polyurethane derivatives, for example those of elasticnature formed from the reaction:

(a1) of at least one cationic unit resulting from at least one tertiaryor quaternary amine bearing at least two reactive functions containinglabile hydrogen,

(a2) of at least one mixture of at least two different nonionic unitsbearing at least two reactive functions containing labile hydrogen, forinstance chosen from hydroxyl groups, primary or secondary amine groups,and thiol groups, and

(b) of at least one compound comprising at least two isocyanatefunctions.

(13) Other cationic polymers that may be used in the context of thedisclosure include, for example, cationic proteins or cationic proteinhydrolysates, polyalkyleneimines, such as polyethyleneimines, polymerscontaining vinylpyridine or vinylpyridinium units, and chitinderivatives.

Particularly useful cationic polymers in the present invention include,but are not limited to, polyquaternium 4, polyquaternium 6,polyquaternium 7, polyquaternium 10, polyquaternium 11, polyquaternium16, polyquaternium 22, polyquaternium 28, polyquaternium 32,polyquaternium-46, polyquaternium-51, polyquaternium-52,polyquaternium-53, polyquaternium-54, polyquaternium-55,polyquaternium-56, polyquaternium-57, polyquaternium-58,polyquaternium-59, polyquaternium-60, polyquaternium-63,polyquaternium-64, polyquaternium-65, polyquaternium-66,polyquaternium-67, polyquaternium-70, polyquaternium-73,polyquaternium-74, polyquaternium-75, polyquaternium-76,polyquaternium-77, polyquaternium-78, polyquaternium-79,polyquaternium-80, polyquaternium-81, polyquaternium-82,polyquaternium-84, polyquaternium-85, polyquaternium-86,polyquaternium-87, polyquaternium-90, polyquaternium-91,polyquaternium-92, polyquaternium-94, and guar hydroxypropyltrimoniumchloride.

Particularly preferred cationic polymers of the present inventioninclude POLYMER JR-125, POLYMER JR-400, Polymer JR-30M hydroxyethylcellulosic polymers (polyquaternium 10) available from AMERCHOL; JAGUARC® 13-S, guar hydroxypropyltrimonium chloride, available from Rhodia;and MERQUAT® 100 and 280, a dimethyl dialkyl ammonium chloride(polyquaternium 6) available from Nalco.

The cationic polymer is generally present in an amount of from greaterthan 0% to about 15%, preferably from about 0.5 to about 10% by weight,and more preferably from about 1 to about 5% by weight, based on thetotal weight of the color base or oxidizing composition.

The color base and oxidizing compositions of the present inventionaccording to the disclosure can also comprise at least one additive usedconventionally in compositions for application onto hair.

“Additive” means a substance that is added, different from the compoundsalready mentioned.

As examples of additives that can be used, non-limiting mentions can bemade of antioxidants or reducing agents, penetrating agents,sequestering agents, perfumes, buffers, dispersants, ceramides,sunscreen agents, preservatives, opacifiers, and antistatic agents.

The oxidizing composition comprising at least one oxidizing agent canfurther comprise at least one fatty substance chosen from theabove-described fatty substance, including the at least one fattysubstance having a viscosity greater than about 50 mm²/s at 40° C. Thus,in some embodiments, the total amount of fatty substances in theoxidizing composition may range from about 1% to about 20% by weight, orsuch as from about 5% to about 20% by weight, or such as from about 10%to about 20% by weight, based on the total weight of the oxidizingcomposition.

According to preferred embodiments of the invention, when the color basecomposition is mixed with the oxidizing composition, the total amount offatty substances is at least about 1.25% by weight and may range up toless than about 50% by weight, or up to about 40% by weight, or up toabout 30% by weight, or up to about 20% by weight, or up to about 10% byweight, based on the total weight of the agent for altering the color ofkeratin fibers formed from the combination of the color base andoxidizing compositions of the present invention.

The color base composition of the present disclosure is in the form of awater-in-oil cream emulsion.

The color base and oxidizing compositions according to the disclosurecan be in various forms, such as in the form of creams or gel-creams.

In preferred embodiments, the process of making the color basecomposition, involves a cold process which does not require the use ofheat while the ingredients are mixed and does not require the use of anemulsifier blade.

In other preferred embodiments, the color base composition does notrequire the presence of a fatty alcohol in order to form an emulsion.When the color base composition does not contain a fatty alcohol, thecolor base composition may be prepared in the absence of heat usingmixing speeds at shearing rates that are lower than the shearing ratesused to prepare conventional/commercial hair color that are typicallyprovided in the form of emulsions.

According to the present disclosure, the process of making the colorbase composition involves the general procedure of:

mixing the acrylates copolymer of the present invention (e.g, Carbopol®Aqua SF-1 or Carbopol® Aqua SF-2) with water using a mixer,

adding an amount of a neutralizing agent, such as ethanolamine, to themixture, in order to neutralize the acrylates polymer (indicated by theformation of a clear solution),

adding a high viscosity fatty substance (mineral oil having a viscositygreater than about 50 mm²/s at 40° C.) while mixing with a chopperblade, wherein the speed of mixing can be increased to ensure propermixing)

optionally, adding more of the high viscosity fatty substance if anemulsion is desired,

adding a short alkyl chain hydroxyl compound (e.g. ethanol),

and adding a pH adjusting agent to obtain the desired pH, if necessary.

The acrylates copolymer may also be pre-neutralized before it iscombined with the other ingredients according to the process above.

The above-described process reduces the amount of time needed to preparea conventional/commercial hair color base composition.

The method of the present disclosure is a method comprising applying theagent for altering the color of keratin fibers according to the presentdisclosure onto the keratin fibers. When an oxidizing composition isrequired, the agent for altering the color of the fibers is formed fromcombining the color base and oxidizing compositions of the presentdisclosure wherein the color is developed at an alkaline or neutral toacidic pH and the oxidizing composition can be added at the moment ofuse or it can be used simultaneously with or sequentially to the colorbase composition.

Upon application and after a resting time on the keratin fibers, forexample, ranging from about 1 to 60 minutes, such as from about 5 to 45minutes, the keratin fibers are rinsed, optionally washed with shampooand rinsed again, then dried.

The agent for altering the color of keratin fibers according to thedisclosure can result from mixing at least the color base and oxidizingcompositions of the present invention, including an oxidizingcomposition comprising at least one oxidizing agent as definedpreviously.

The oxidizing composition may be in the form of a powder, gel, liquid,foam, lotion, cream, mousse, and emulsion.

In one embodiment, the oxidizing composition is substantially anhydrous.

The term “substantially anhydrous” means that the oxidizing compositionis either completely free of water or contains no appreciable amount ofwater, for example, no more than 5% by weight, or no more than 2% byweight, or no more than 1% by weight, based on the weight of theoxidizing composition. It should be noted that this refers for exampleto bound water, such as the water of crystallization of the salts ortraces of water absorbed by the raw materials used in the preparation ofthe compositions according to the disclosure.

The oxidizing composition can contain at least one solvent, chosen fromwater, organic solvents, and mixtures thereof.

When the oxidizing composition is substantially anhydrous, the oxidizingcomposition may comprise at least one solvent chosen from organicsolvents.

Suitable organic solvents for use in the oxidizing composition includeethanol, isopropyl alcohol, benzyl alcohol, phenyl ethyl alcohol,glycols and glycol ethers, such as propylene glycol, hexylene glycol,ethylene glycol monomethyl, monoethyl or monobutyl ether, propyleneglycol and its ethers, such as propylene glycol monomethyl ether,butylene glycol, dipropylene glycol, diethylene glycol alkyl ethers,such as diethylene glycol monoethyl ether and monobutyl ether,hydrocarbons such as straight chain hydrocarbons, mineral oil,polybutene, hydrogenated polyisobutene, hydrogenated polydecene,polydecene, squalane, petrolatum, isoparaffins, and mixtures, thereof.

The at least one solvent may, for example, be present in an amountranging from about 0.5% to about 70% by weight, such as from about 2% toabout 60% by weight, preferably from about 5 to about 50% by weight,relative to the total weight of the oxidizing composition.

The pH of the oxidizing composition can range from about 2 to about 12,such as from about 6 to about 11, and it may be adjusted to the desiredvalue using acidifying/alkalizing agents that are well known in the art.

According to one embodiment of the invention, the agent for altering thecolor of keratin fibers is a composition comprising, in a cosmeticallyacceptable medium, at least one fatty substance having a viscositygreater than about 50 mm²/s at 40° C., optionally, at least oneadditional fatty substance, at least one rheology modifying polymerchosen from: (i) a slightly alkali-swellable cross-linked acrylatepolymer contained in an aqueous dispersion comprising about 30% byweight of total solids and (ii) a cross-linked anionic acrylate polymercontained in an aqueous dispersion comprising about 32% by weight oftotal solids, at least one alkalizing agent, at least one short chainhydroxyl compound chosen from monoalcohols and polyols; at least onedirect dye; optionally, at least one oxidative dye precursor; atoptionally, least one oxidizing agent, and wherein the pH of the agentfor altering the color of keratin fibers is from between about 2 toabout 14.

According to another embodiment of the invention, the agent for alteringthe color of keratin fibers can comprise two compositions, a color basecomposition, containing, in a cosmetically acceptable medium, at leastone fatty substance having a viscosity greater than about 50 m^(m2)/s at40° C., optionally, at least one additional fatty substance, at leastone rheology modifying polymer as defined previously, at least onealkalizing agent; and at least one short chain hydroxyl compound chosenfrom monoalcohols and polyols; at least one direct dye; optionally, atleast one oxidative dye precursor; and a second unit of an oxidizingcomposition containing, in a cosmetically acceptable medium, at leastone oxidizing agent, and wherein the agent for altering the color ofkeratin is from between about 2 to about 14.

According to yet another embodiment of the invention, the agent foraltering the color of keratin fibers can result from mixing two units,including a first unit of a color base composition, containing, in acosmetically acceptable medium, at least one fatty substance having aviscosity greater than about 50 mm²/s at 40° C., optionally, at leastone additional fatty substance, at least one rheology modifying polymeras defined previously, at least one alkalizing agent; and at least oneshort chain hydroxyl compound chosen from monoalcohols and polyols; anda second unit of an oxidizing composition containing, in a cosmeticallyacceptable medium, at least one oxidizing agent, and wherein the agentfor altering the color of keratin fibers is greater than about 7.

It has been surprisingly discovered that the combination of the fattysubstance having a viscosity greater than about 50 mm²/s at 40° C., andthe rheology modifying polymer as defined previously results in a stablewater-in-oil liquid emulsion composition which, when used alone or whencombined with the oxidizing composition, provides a ready-to-use haircolor with a non-drip consistency that is still easy to spread onkeratin fibers, such as hair.

It has also been discovered that the application of the agent foraltering the color of keratin fibers onto the fibers results insatisfactory coloring of the fibers while utilizing lower amounts of theoxidizing agent compared to conventional oxidative dyeing compositions.

According to another embodiment of the invention, a kit for coloringkeratin fibers is provided, comprising a first unit containing the abovedescribed color base composition and a second unit comprising the abovedescribed oxidizing composition when oxidative dye precursors are usedin the color base composition.

According to another embodiment of the invention, a kit for coloringkeratin fibers is provided, comprising a first unit containing the abovedescribed color base composition and a second unit comprising the abovedescribed color base composition.

The coloring obtained using the compositions and method of the presentdisclosure may also be durable or wash/fade resistant.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the disclosure are approximations, unless otherwiseindicated the numerical values set forth in the specific examples arereported as precisely as possible. Any numerical value, however,inherently contains certain errors necessarily resulting from thestandard deviation found in their respective testing measurements.

The examples that follow serve to illustrate embodiments of the presentdisclosure without, however, being limiting in nature.

EXAMPLES Example 1 Formulation Examples

The following comparative direct dye compositions and liquid emulsioncolor base compositions were prepared:

Modified Comparative inventive dye Inventive color composition* colorbase** base*** INGREDIENTS (INCI NAMES) Formula A Formula B Formula CETHANOLAMINE — 4 4 Acrylates Copolymer — 2.55 2.55 (Carbopol ® AquaSF-1) MINERAL OIL (high — 50 50 viscosity)^(a) ALCOHOL DENAT. — 10 10 HCRED NO. 3 0.6 0.6 0.3 HC YELLOW NO. 9 0.2 0.2 0.1 4-AMINO-3-NITROPHENOL0.4 0.4 0.2 3-NITRO-P- 0.3 0.3 0.15 HYDROXYETHYLAMINOPHENOL FATTY ACID,NONIONIC 5.8 — — SURFACTANTS, ALKOXYLATED AMIDE GLYCOLS/POLYHYDROXY 6.5— — COMPOUNDS SODIUM METABISULFITE 0.5 0.5 AMINOMETHYL PROPANOL 0.6 — —ERYTHORBIC ACID 0.3 0.3 HYDROXYETHYLCELLULOSE 1.2 — — WATER q.s. 100q.s. 100 q.s. 100 *Comparative Dye Composition **Inventive color base -contains approximately the same total amount of dyes as the comparativedye composition ***Modified inventive color base - total amount of dyesis less than that of the comparative dye composition ^(a)viscosity fromabout 63 to about 70 mm²/s at 40° C.; commercially available from thesupplier Sonneborn under the tradename Kaydol ® Heavy White Mineral Oilor from the supplier Exxonmobil Chemical under the tradename Primol ™352

The cream emulsion formula above was prepared as follow (1000 grams intotal):

Acrylates Copolymer (commercially available as Carbopol® Aqua SF-1) wasadded to water and the resulting solution was mixed using a VMI Raynerimixer equipped with a chopper blade. 10 g of Ethanolamine was added toneutralize the acrylates copolymer. The solution became a clear thickgel upon complete neutralization. The speed of mixing was increased toat least about 600 rpm. The solution became thicker & turned into awhite paste. 80 g of mineral oil was added to the solution to create anemulsion and the speed of mixing was increased to at least about 1000RPM. One half of the remainder of the oil (remainder of 420 grams), wasthen added to the emulsion and mixing was continued for about 10minutes. The speed of mixing was increased to at least about 1200 RPM toensure proper mixing. One half of the total concentration of alcoholdenatured (ethanol) required was added to adjust or decrease theviscosity of the emulsion. The remainder of the mineral oil was thenadded and mixing was continued for a few minutes. If an additional fattysubstance other than the fatty substance having a viscosity of greaterthan about 50 mm²/s at 40° C. is employed, it can also be added at thisstage, together with other additives that may be desired. The remainderof the alcohol denatured was also added. The anti-oxidants, sodiummetabisulfite and erythorbic acid, were added to the emulsion. The speedof mixing was decreased. The remainder of the ethanolamine was added tothe emulsion to adjust the pH. An acidifying or basifying agent wasadded to the emulsion to further adjust the pH, if necessary.

It was found that even when high levels of mineral oil are incorporatedinto the formulas above, the formulas remained stable and in creamemulsion form.

When oxidative dyes are employed in the color base composition, anoxidizing composition is required. The following is a formulationexample of the oxidizing composition:

Phases Ingredients (INCI Name) % by weight A CETEARYL ALCOHOL 6 ASTEARETH-20 5 A MINERAL OIL (Low viscosity)* 20 A PEG-4 RAPESEEDAMIDE1.2 A BHT 0.0012 A TOCOPHEROL 0.1 B WATER 59.2 B GLYCERIN 0.5 BPENTASODIUM PENTETATE 0.06 B POLYQUATERNIUM-6 0.2 B HEXADIMETHRINECHLORIDE 0.15 C TETRASODIUM PYROPHOSPHATE 0.03 C SODIUM STANNATE 0.04 DPHOSPHORIC ACID To adjust the pH D HYDROGEN PEROXIDE 7.5 Total 100*viscosity at about 30 mm²/s at 40° C.

The oxidizing composition above was prepared as follows:

Cetearyl Alcohol, Steareth-20, Mineral Oil, PEG-4 Rapeseedamide, andTocopherol were added to a main beaker and heated to 80° C. (Phase A).Water was heated to 80° C. and added to phase A to form a solution. Thesolution was homogenized for 10 minutes at 2500 RPM. Glycerin,Pentasodium Pentetate, Polyquaterium-6, Hexadimethrine Chloride werethen added to the solution and mixed for 10 minutes. Phase A was thencooled to 25° C. Hydrogen Peroxide was added to the solution andhomogenized for 5 minutes. The homogenizer blade was removed andreplaced with a chopper blade. Phosphoric Acid was added to adjust thepH to 2.0-2.40.

Example 2 Hair Coloration Studies; Colorimetric Measurements

If oxidative dyes are not employed, the color base composition serves asthe agent for altering the color of hair (or ready-to-use composition)and is applied directly onto hair.

If oxidative dyes are employed, the agent for altering the color of hairwas prepared by mixing the color base composition, and an oxidizingcomposition and was used to color hair at the time of use in thefollowing manner:

-   -   10 g of the dye base composition A was mixed with 10 g of the        oxidizing composition B;    -   the resulting mixture resulting was applied onto hair swatches;    -   the hair swatches were then washed with shampoo, rinsed and then        dried.

If desired, the color base composition can be mixed with the oxidizingcomposition in a 1:1 ratio, or a 1:2 ratio or a 1:3 ratio.

Each of the color base formulas in Example 1 above was mixed with anoxidizing composition to form the agent for altering the color of hair(swatches). After dyeing the hair, the color of the swatches wasmeasured with a Minolta CM2600d spectrocolorimeter (specular componentsincluded, 10 degrees angle, illuminant D65) in the CIEL*a*b* system. Inthis system, L* represents the intensity of the color, a* indicates thegreen/red color axis and b* the blue/yellow color axis.

According to this system, the greater the value of L, the lighter orless intense the color. Conversely, the lower the value of L, the darkeror more intense the color.

DELTA E represents the change in color between a control hair swatch(undyed/untreated) and a treated (or dyed) hair swatch, and isdetermined from the change in L* values, a* values and b* values.

The colorimetric results obtained are given in the table below.

90% gray HAIR DYE TYPE^(a) Shade Formula hair type L* CIE76 DE Virgin -Unpermed — — — 59.96 4.00 Std. Comparative dye Red Formula A Unpermed32.14 3.72 composition Inventive color Red Formula B Unpermed 24.78 9.18base Modified Red Formula C Unpermed 25.21 25.21 inventive color baseVirgin - Permed — — — 57.77 1.7 Std. Comparative dye Red Formula APermed 28.46 1.02 composition Inventive color Red Formula B Permed 20.2114.01 base Modified Red Formula C Permed 21.22 11.33 inventive colorbase ^(a)formula plus oxidizing composition L* represents lightness orintensity of color; the higher the L value, the lighter the color of thehair. Delta-E (DE) represents the difference between two colors. If DEis less than 1.0 there is hardly any color difference that the human eyecan perceive. If DE is greater than 1.0 there is a noticeable colordifference by eye.

The results above show that the hair treated with the inventive dyeingcompositions were significantly darker than the hair treated with thecomparative formula which means that the inventive compositionsdeposited a more intense red color compared to the comparative dyecomposition. Moreover, the inventive color base formulas which had atleast a 50% reduction in the amount of dye compounds compared to thecomparative dye composition still yielded a greater color deposit(smaller L value) than the comparative dye composition, indicating thatthe amount of dyes can still be further reduced in the inventivecompositions allowing for greater cost reduction and lessstability/suspension problems with the dye compounds. The same resultswere observed for both unpermed and permed hair.

Example 3 Suspension/Stability Studies

The color base formulas of the present invention were tested forstability using yield stress measurements (elastic function, G′ (Pa))over increasing temperature from 20° C. to 60° C. (temperature sweep of1 degree C. per minute, at 0.1% deformation). Stability of the dyecompositions is also related to the ability of the compositions tosuspend the dye molecules without becoming unstable over increasingtemperatures or over time.

It will be apparent to those skilled in the art that variousmodifications and variations can be made in the delivery system,composition and methods of the invention without departing from thespirit or scope of the invention. Thus, it is intended that the presentinvention cover the modifications and variations of this inventionprovided that they come within the scope of the appended claims andtheir equivalents.

What is claimed is:
 1. An agent for altering the color of keratin fiberscomprising: (A) a color base composition, containing, in a cosmeticallyacceptable medium: (a) from about 50% to about 80% by weight of a fattysubstance comprising: (i) at least 5% by weight of at least one fattysubstance having a viscosity greater than about 50 mm²/s at 40° C.; and(ii) from 0% to about 75% by weight of at least one additional fattysubstance other than (A)(a); all weights being based on the total weightof (A); (b) at least one rheology modifying polymer chosen from: (i) aslightly cross-linked, alkali-swellable acrylate polymer contained in anaqueous dispersion comprising about 30% by weight of total solids; and(ii) a cross-linked anionic acrylate polymer contained in an aqueousdispersion comprising about 32% by weight of total solids; and (c) atleast one alkalizing agent; (d) at least one short alkyl chain hydroxycompound chosen from monoalcohols and polyols; (e) at least one directdye; (f) optionally, at least one oxidative dye precursor; and (B)optionally, an oxidizing composition comprising, in a cosmeticallyacceptable medium, at least one oxidizing agent.
 2. The agent accordingto claim 1, wherein (A)(a)(i) has a viscosity ranging from betweengreater than about 50 to about 100 mm²/s at 40° C.
 3. The agentaccording to claim 1, wherein (A)(a)(i) comprises mineral oil having aviscosity ranging from about 63 to about 70 mm²/s at 40° C.
 4. The agentaccording to claim 1, wherein (A)(a)(i) is present in an amount of fromabout 50% to about 70% by weight, based on the total weight of (A). 5.The agent according to claim 1, wherein (A)(a)(i) is present in anamount of from about 50% to about 60% by weight, based on the totalweight of (A).
 6. The agent according to claim 1, wherein (A)(a)(ii) ischosen from C₆-C₁₆ lower alkanes, non-silicone oils of mineral, plant,animal and synthetic origin, fatty alcohols, fatty acid esters, fattyalcohol esters, fatty acids, non-silicone waxes and silicones.
 7. Theagent according to claim 1, wherein (A)(b) comprises acrylatescopolymer.
 8. The agent according to claim 1, wherein (A)(b) comprisesacrylates crosspolymer-4.
 9. The agent according to claim 1, wherein(A)(b) is present in an amount of from about 0.3% to about 3% by weight,based on the total weight of (A).
 10. The agent according to claim 1,wherein (A)(b) is present in an amount of from about 0.45% to about2.75% by weight, based on the total weight of (A).
 11. The agentaccording to claim 1, wherein (A)(b) is present in an amount of fromabout 0.5% to about 2% by weight, based on the total weight of (A). 12.The agent according to claim 1, wherein the weight ratio of (a) to (b)in (A) ranges from about 25:1 to about 3:1.
 13. The agent according toclaim 1, wherein the weight ratio of (a) to (b) in (A) ranges from about15:1 to about 10:1.
 14. (canceled)
 15. The agent according to claim 1,wherein (A)(c) is chosen from alkali metal carbonates, alkali metalphosphate, organic amines, hydroxide base compounds, and derivativesthereof.
 16. The agent according to claim 1, wherein (A)(c) is chosenfrom ethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, andmixtures thereof.
 17. The agent according to claim 1, wherein (A)(c) ispresent in an amount of from about 0.01% to about 30% by weight, basedon the total weight of (A).
 18. The agent according to claim 1, wherein(A)(c) is present in an amount of from about 0.5% to about 5% by weight,based on the total weight of (A).
 19. The agent according to claim 1,wherein (A)(d) is chosen from ethanol, propanol, ethylene glycol,propylene glycol, butylene glycol, hexylene glycol, propane diol, andmixtures thereof.
 20. The agent according to claim 1, wherein (A)(d) ispresent in an amount of from about 0.5% to about 15% by weight, based onthe total weight of (A).
 21. The agent according to claim 1, wherein(A)(d) is present in an amount of from about 5% to about 10% by weight,based on the total weight of (A).
 22. The agent according to claim 1,wherein (A)(e) is chosen from neutral, acidic, or cationic nitrobenzenedyes; neutral, acidic, or cationic azo direct dyes; neutral, acidic, orcationic quinone and anthraquinone direct dyes; azine direct dyes;triarylmethane direct dyes; indoamine direct dyes; and natural directdyes.
 23. The agent according to claim 1, wherein (A)(e) is present inan amount of from about 0.001% to about 20% by weight, based on thetotal weight of (A).
 24. The agent according to claim 1, wherein (A)(f)is chosen from oxidation bases and couplers, and mixtures thereof. 25.The agent according to claim 1, wherein (A)(f) is chosen from ortho- andpara-phenylenediamine oxidation bases, double bases, ortho- andpara-aminophenols, heterocyclic bases, as well as salts of addition ofthese compounds with an acid and meta-aminophenol,meta-phenylenediamine, meta-diphenol, naphthol couplers, heterocycliccouplers and acid salts thereof.
 26. The agent according to claim 1,wherein the pH of (A) ranges from about 7.5 to about
 14. 27. The agentaccording to claim 1, wherein the pH of (A) ranges from about 9 to about11.
 28. The agent according to claim 1, wherein the at least oneoxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkalimetal bromates, ferricyanides, peroxygenated salts, perborates,percarbonates, laccases, peroxidases, redox enzymes, and mixturesthereof.
 29. The agent according to claim 1, wherein the at least oneoxidizing agent is present in an amount of from about 0.05% to about 50%by weight, based on the total weight of (B).
 30. The agent according toclaim 1, wherein the at least one oxidizing agent is present in anamount of from about 1% to about 12% by weight, based on the totalweight of (B).
 31. The agent according to claim 1, wherein the pH of theagent ranges from about 1 to about
 7. 32. The agent according to claim1, wherein the pH of the agent ranges from about 7.1 to about
 14. 33.The agent according to claim 1, wherein (A) further comprises at leastone neutralizing agent chosen from ethylamines, ethyleneamines,alkanolamines, cyclic amines and other cyclic compounds, saturated orunsaturated, having one or more nitrogen atoms within the ring.
 34. Theagent according to claim 1, wherein (A) and/or (B) further comprises atleast one auxiliary agent chosen from thickening agents and rheologymodifying polymers other than (A)(b), cationic polymers, film formingpolymers, pigments, dyes, humectants and moisturizing agents,emulsifying agents other than those that fall under the above-describedfatty substances, structuring agents, propellants, surfactants, shineagents, and conditioning agents.
 35. The agent according to claim 1,wherein (B) further comprises at least one fatty substance chosen from afatty substance having a viscosity greater than about 50 mm²/s at 40°C., an additional fatty substance other than the fatty substance havinga viscosity greater than about 50 mm²/s at 40° C., and mixtures thereof.36. The agent according to claim 1, wherein the agent for altering thecolor of keratin fibers is substantially free of ammonia.
 37. The agentaccording to claim 1, wherein the agent is a hair coloring ready-to-usecomposition.
 38. A process for coloring keratin fibers, comprising: (A)applying onto keratin fibers, an agent for altering the color of keratinfibers comprising a color base composition, containing, in acosmetically acceptable medium: (a) from about 50% to about 80% byweight of a fatty substance comprising: (i) at least 5% by weight of atleast one fatty substance having a viscosity greater than about 50 mm²/sat 40° C.; and (ii) from 0% to about 75% by weight of at least oneadditional fatty substance other than (A)(a)(i); all weights being basedon the total weight of (A); (b) at least one rheology modifying polymerchosen from: (i) a slightly cross-linked, alkali-swellable acrylatepolymer contained in an aqueous dispersion comprising about 30% byweight of total solids; and (ii) a cross-linked anionic acrylate polymercontained in an aqueous dispersion comprising about 32% by weight oftotal solid; and (c) at least one alkalizing agent; (d) at least oneshort alkyl chain hydroxy compound chosen from monoalcohols and polyols;(e) at least one direct dye; and (B) leaving the agent on the keratinfibers for a period of time sufficient to achieve a desired change inthe color of the fibers.
 39. The process of claim 38, wherein the colorbase composition further comprises at least one oxidative dye precursorchosen from oxidation bases and couplers, and mixtures thereof.
 40. Theprocess of claim 39, wherein the agent for altering the color of keratinfibers further comprises an oxidizing composition comprising, in acosmetically acceptable medium, at least one oxidizing agent.
 41. Theprocess of claim 40, wherein the agent for altering the color of keratinfibers is formed by mixing the color base composition and the oxidizingcomposition.
 42. A kit comprising a unit containing a color basecomposition, containing, in a cosmetically acceptable medium: (a) fromabout 50% to about 80% by weight of a fatty substance comprising: (i) atleast 5% by weight of at least one fatty substance having a viscositygreater than about 50 mm²/s at 40° C.; and (ii) from 0% to about 75% byweight of at least one additional fatty substance other than (a)(i); allweights being based on the total weight of (A); (b) at least onerheology modifying polymer chosen from: (i) a slightly cross-linked,alkali-swellable acrylate polymer contained in an aqueous dispersioncomprising about 30% by weight of total solids; and (ii) a cross-linkedanionic acrylate polymer contained in an aqueous dispersion comprisingabout 32% by weight of total solid; and (c) at least one alkalizingagent; (d) at least one short alkyl chain hydroxy compound chosen frommonoalcohols and polyols; (e) at least one direct dye
 43. The kit ofclaim 42, wherein the color base composition further comprises at leastone oxidative dye precursor chosen from oxidation bases and couplers,and mixtures thereof.
 44. The kit of claim 43, further comprising anadditional unit containing an oxidizing composition comprising, in acosmetically acceptable medium, at least one oxidizing agent.
 45. Anagent for altering the color of keratin fibers comprising, in acosmetically acceptable medium: (a) from about 10% to less than about50% by weight, based on the total weight of the agent, of at least onefatty substance having a viscosity greater than about 50 mm²/s at 40°C.; (b) from about 0.3% to about 3% by weight, based on the total weightof the agent, of at least one rheology modifying polymer chosen from:(i) a slightly cross-linked, alkali-swellable acrylate polymer containedin an aqueous dispersion comprising about 30% by weight of total solids;and (ii) a cross-linked anionic acrylate polymer contained in an aqueousdispersion comprising about 32% by weight of total solids; (c) at leastone alkalizing agent; (d) from about 0.5% to about 15% by weight, basedon the total weight of the agent, of at least one short chain hydroxylcompound chosen from monoalcohols and polyols; (e) at least one directdye; (f) optionally, at least one oxidative dye precursor; andoptionally, at least one oxidizing agent.